Probabilistic Safety Assessment in the Chemical and Nuclear Industries

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Author: Ralph Fullwood Attended Texas Technological University Harvard University University of Pennsylvania and Rensselaer Polytechnic Institute.

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Probabilistic Safety Assessment in the Chemical and Nuclear Industries

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Probabilistic Safety Assessment in the Chemical and Nuclear Industries

Ralph R. Fullwood

• »1U T T E R W O R T H |S|E 1 N E M A N N

Boston Oxford Auckland Johannesburg Melbourne New Delhi

Copyright €> 2000 by Butterworth-Heinemann member of the Reed Elsevier group All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without the prior written permission of the publisher. Recognizing the importance of preserving what has been written, Butterworth-Heinemann prints its books on acid-free paper whenever possible. Butterworth-Heinemann supports the efforts of American Forests and the Global ReLeaf program in its campaign for the betterment of trees, forests, and our environment. Library of Congress Cataloging-in-Publication Data Fullwood, R. R. Probabilistic safety assessment in the chemical and nuclear industries / Ralph R. Fullwood. p. cm. Rev. edition of: Probabilistic risk assessment in the nuclear power industry, 1988. ISBN 0-7506-7208-0 (alk. paper) 1, Nuclear power plants—Risk assessment. 2. Chemical plants—Risk assessment. I. Title. TK9153.F8531999 99-37453 363.17'992—dc21 CIP British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library. The publisher offers special discounts on bulk orders of this book. For information, please contact: Manager of Special Sales Butterworth-Heinemann 225 Wildwood Avenue Woburn, MA 01801-2041 Tel: 781-904-2500 Fax: 781-904-2620 For information on all Butterworth-Heinemann publications available, contact our World Wide Web home page at: http://www.bh.com 10987654321 Printed in the United States of America

Disclaimer The information in this book is collected from published and unpublished literature. Responsibility for the accuracy of this material is disclaimed, however, responsibility is accepted for the selection, organization, and presentation. The vastness of the information necessitates selectivity in the attempt to make a comprehensive and cohesive presentation. The material is selected to illustrate a procedure or principle not advocacy. Every effort toward objectivity was made to balance human health and safety, environment, economic welfare, and civilization. Neither I, Brookhaven National Laboratory from which I am retired, nor the publisher are responsible for the materials presented here. RALPH R. FULL WOOD Upton, NY October 1998


Contents Chapter I Protecting the Public Health and Safety , 1.1 Historical Review 1.1.1 Beginnings 1.1.2 Industrial Revolution 1.1.3 This Century .,2 Risk Assessment Objectives 1.3 Risk, Hazard, and other Terms 1.4 Quantitative Aspects of Risk 1.4.1 Actuarial or Linear Risk 1.4.2 Shortcomings of Linear Risk 1.4.3 Presentation of Risk 1.4.4 Public Perception of Risk 1.5 Safety Goals 1.6 Emergency Planning Zones 1.7 Use of PSA by Government and Industry 1.8 Regulation of Nuclear Power 1.8.1 Regulations 1.8.2 Regulatory Structure 1.8.3 Licensing Process 1.8.4 Public Participation 1.8.5 Advisory Committee on Reactor Safety (ACRS) 1.8.6 Inspection 1.8.7 Decommissioning 1.8.8 Accident Severity Criteria , 1.8.9 PSA Requirements 1.9 Regulation of Chemical Processing and Wastes 1.9.1 Environmental Law 1.9.2 Occupational Risk Protection: the PSM Rule 1.10 Summary 1.11 Problems Chapter 2. 2.1 2.2 2.3 2.4

Mathematics for Probabilistic Safety Boolean Algebra Venn Diagram and Mincuts Probability and Frequency Combining Probabilities 2.4.1 Intersection or Multiplication 2.4.2 Union or Addition 2.4.3 M-Out-of-N-Combinations 2.5 Distributions 2.5.1 Discrete Distributions vn

1 ,i .I 2 ....... 3 , .... 5 .....,,,., 6 6 , , 6 , ....7 ....,.,..,,..8 , 12 13 15 17 , 18 18 18 19 20 20 ..21 21 .21 22 . 22 22 27 33 34 , ,..,,,.,

35 35 37 39 4! 41 41 42 42 43

2.5.2 Continuous Distributions . 2.5.3 Confidence Limits 2.5.4 Markov Modeling 2.5.5 Summary of Functions and their Generating Functions 2.6 Bayesian Methods 2.6.1 Bayes' Equation 2.6.2 Bayes Conjugates for Including New Information 2.6.3 Constant Failure Rate Model 2.6.4 Failure on Demand Model 2.6.5 Interpretations of Bayes Statistics 2.7 Uncertainty Analysis . 2.7.1 Convolution 2.7.2 Moments Method . 2.7.3 Taylor's Series 2.7.4 Monte Carlo . 2.7.5 Discrete Probability Distribution (DPD) 2.8 Sensitivity Analysis and Importance Measures 2.8.1 Sensitivity Analysis 2.8.2 Importance Measures 2.8.3 Relationships between the Importance Measures 2.8.4 Interpretation and Usage 2.9 Summary 2.10 Problems Chapter 3 Chemical and Nuclear Accident Analysis Methods 3.1 Guidance from the PSM Rule 3.1.1 Rule Objectives 3.1.2. Employee Involvement in Process Safety 3.1.3. Process Safety Information 3.2 Process Hazard Analysis 3.2.1 Overview 3.2.2 Operating Procedures and Practices 3.2.3. Employee Training 3.2.4 Contractors 3.2.5 Pre-Startup Safety 3.2.6 Mechanical Integrity 3.2.7 Nonroutine Work Authorization 3.2.8 Managing Change 3.2.9 Investigation of Incidents 3.2.10 Emergency Preparedness . 3.2.11 Compliance Audits . 3.3 Qualitative Methods of Accident Analysis 3.3.i Checklist Vlll

,

44 . 47 48 49 50 50 51 52 54 55 56 56 57 57 59 60 61 61 62 63 64 65 . . . . . . . . . 66 67 67 67 67 68 70 70 71 71 71 72 72 73 ,73 . 74 74 75 76 77

3.3.2 What-If Analysis 81 3.3.3 What-If/Checklist Analysis . . . 84 3.3.4 Hazard and Operability (HAZOP) 86 3.3.5 Failure Mode and Effects Analysis 94 3.4 Quantitative Methods of Accident Analysis 97 3.4.1 Parts Count 98 3.4.2 FMEA/FMECA . , 99 3.4.3 Reliability Block Diagram (RED). 100 3.4.4 Fault Tree Analysis 101 3.4.5 Event Trees . . . . . . . . . 111 3.4.6 Alternatives to Fault Tree Analysis 119 3.5 Common Cause of Failure 123 3.5.1 Known Deterministic Coupling 124 3.5.2 Known Stochastic Coupling 125 3.5.3 Unknown Stochastic Coupling 125 3.5.4 Modeling Known Dependencies ....,,, , . 125 3.5.5 Geometric Mean 126 3.5.6 Beta Factor 126 3.5.7 Example of the Beta-Factor Method: Emergency Electric Power . . . . . . 127 3.5.8 Common Cause Multiparameter Models .127 3.6 Computer Codes for System Reliability Analysis 128 3.6.1 Codes for Finding Minimal Cutsets and Tree Quantification . 130 3.6.2 Truncation of a Fault Tree 133 3.6.3 Time Dependence 134 3.6.4 Uncertainty Analysis 134 3.6.5 Importance Calculations 134 3.6.6 Processing Cutset Information , . . 135 3.6.7 System Analysis Code Usage in Past PSAs 136 3.6.8 Logistics of Acquiring Codes . . . . . . , , , . 136 3.7 Code Suites ., 136 3.7.1 SAPHIRE 136 3.7.2 PSAPACK 141 3.7.3 RISKMAN . 143 3.7.4 R&R Workstation 144 3.7.5 WinNUPRA, NUCAP+, and SAFETY MONITOR 145 3.8 Summary 147 3.9 Problems 148 Chapter 4 Failure Rates, Incidents and Human Factors Data 4.1 Databases , 4.1.1 Background 4.1.2 Some Reliability Data Compilations 4.2 Incident Reports IX

151 151 151 151 158

4.3 Database Preparation 4.3.1 How to Estimate Failure Rates 4.3.2 Making a Database 4.3.3 Test Reports and Procedures 4.3.4 Maintenance Reports 4.3.5 Operating Procedures 4.3.6 Control Room Log 4.3.7 Information Flow in Plant Data Collecting 4.3.8 Data Sources Used in Past PSAs 4.4 Human Reliability Analysis 4.4.1 Human Error in System Accidents 4.4.2 Lack of Human Error Considerations 4.4.3 Cases Involving Human Error 4.5 Incorporating Human Reliability into a PSA 4.5.1 Human Reliability Analysis Models 4.5.2 Quantifying Human Error Probabilities (HEPs) 4.5.3 Human Factors Data 4.5.4 Example of Human Error Analysis 4.5.5 HRA Event Tree (NUREG/CR-1278) 4.5.6 Comparison of Human Factors in PSAs 4.7 Summary 4.8 Problems

....,,.,,.,

160 ... 160 . 160 , 161 162 . . . , . , . 162 162 163 .163 163 163 166 168 173 173 175 179 180 ............181 183 , 184 . . 184

Chapter 5 External Events 5.1 Seismic Events 5.1.1 Overview 5.1.2 Richter Magnitude - Frequency of Occurrence Distribution 5.1.3 Ground Coupling with Attenuation 5.1.4 Shaking Model of the Plant 5.1.5 Fragility Curves 5.1.6 System Analysis 5.2 Fires 5.2.1 Introduction 5.2.2 Procedures for Fire Analysis 5.2.3 Screening Analysis 5.2.4 Fire Frequencies 5.2.5 Fire Growth Modeling 5.2.6 Fragility Curves 5.2.7 Systems Analysis 5.3 Flood 5.3.1 Overview of Internal Flooding 5.3.2 Internal Flooding Incidents 5.3.3 Internal Flood Modeling

. 185 185 185 188 190 190 192 194 195 195 196 197 197 198 199 199 200 200 200 202

5.3.4 External Flooding 5.4 Summary . . . .

, , 203 . . . . . . . . . 204

Chapter 6 Analyzing Nuclear Reactor Safety Systems . , , , , . , 205 6.1 Nuclear Power Reactors 205 6.1.1 U.S. Light Water Reactors 206 6.1.2 Pressurized Water Reactors . . , . . , . , . . , , . 208 6.1.3 Boiling Water Reactors ..............211 6.1.4 Advanced Light Water Reactors 213 6.2 TMI-2 and Chernobyl Accidents 221 6.2.1 The TMI-2 Accident 221 6.2.2 The Chernobyl Accident 223 6.3 Preparing a Nuclear Power Plant PSA 227 6.3.1 Overview of the Probabilistic Safety Process Using Event Trees 228 6.3.2 Preparing for the PSA 228 6.3.3 PSA Construction 236 6.4 Example: Analyzing an Emergency Electric Power System 238 6.4.1 The Problem: Emergency Electric Power 239 6.4.2 Overview of FTAPSUIT 239 6.5 Summary 243 6.6 Problems 243 Chapter 7 Analyzing Chemical Process Safety Systems 245 7.1 Chemical Process Accidents . . . . . . . . , , . , . 245 7.1.1 The Nature of Process Accidents 245 7.1.2 Some Deadly and Severe Chemical Accidents 247 7.2 Chemical Processes 261 7.2.1 The Topography of Chemical Processes 261 7.2.2 Inorganic Chemicals 262 7.2.3 Fertilizer Production 264 7.2.4 Halogens and Their Compounds 266 7.2.5 Organic Chemicals . . . , , . , . , 269 7.2.6 Explosives 272 7.2.7 Plastics and Resins 276 7.2.8 Paints and Varnishes 283 7.2.9 Petrochemical Processing 286 7.3 Chemical Process Accident Analysis 293 7.3.1 Scoping Analysis 295 7.3.2 Performing a Detailed Probabilistic Safety Analysis 299 7.4 Example: Analyzing a Chemical Tank Rupture 304 7.4.1 Defining the Problem with Fault Tree Analysis 304 7.4.2 Applying FTAPSUIT to Chemical Process Tank Rupture 305 7.5 Summary , 307

XI

7,6 Problems , 308 Chapter 8 Nuclear Accident Consequence Analysis 3O> 8.1 Meltdown Process $09 8.1.1 Defense in Depth Barriers Providing Public Protection , . . . . , , 109 8.1.2 Qualitative Description of Core Melt ^10 8.2 Source Terms for In-Plant Radionuclide Transport , 314 8.2.1 Background on the Source Term 314 8.2.2 Computer Codes for Fission Product Release and In-Plant Transport . 316 8.2.3 Comparison with WASH-1400 . . . . 320 8.3 Ex-Plant Transport of Radionuclides , ^21 8.3.1 Atmospheric Transport Models . . . . . . . , , 321 8.3.2 Health Effects . . 323 8.3.3 Radiation Shielding and Dose 325 8.3.4 Computer Codes for Consequence Calculation . . . . . . . . . . . . . . . . . . . 32Q 8.3.5 Aquatic Transport 331 8.4 Summary ,.331 8.5 Problems 331 Chapter 9 Chemical Process Accident Consequence Analysis 333 9.1 Hazardous Release 333 9.1.1 Pipe and Vessel Rupture 333 9.1.2 Discharge through a Pipe 335 9.1.3 Gas Discharge from a Hole in a Tank 337 9.1.4 Liquid Discharge from a Hole in a Tank 338 9.1.5 Unconfined Vapor Cloud Explosions (UVCE) 338 9.1.6 Vessel Rupture (Physical Explosion) 342 9.1.7 BLEVE, Fireball and Explosion 343 9.1.8 Missiles . 345 9.2 Chemical Accident Consequence Codes 346 9.2.1 Source Term and Dispersion Codes 347 9.2.2 Explosions and Energetic Events 362. 9.2.3 Fire Codes 365 9.3 EPA's Exposure Model Library and Integrated Model Evaluation System . . . . . . . 368 9.3.1 IMES 368 9.3.2 PIRANHA 371 9.3.3 REACHSCN 371 9.3.4 SIDS 371 9.3.5 THERDCD 372 9.4 Summary . 373 Chapter 10 Assembling and Interpreting the PSA 10.1 Putting It Together 10.1.1 Integrated and Special PSAs XII

375 375 375

10.1.2 Assembling the PSA 10.2 Insights and Criticisms 10.2.1 Insights from Past PSAs 10.2.2 Criticism of Past PSAs

,

375 . 377 378 . 378

Chapter 11 Applications of PSA 383 11.1 U.S. Commercial Nuclear PSAs 383 11.1.1 Commercial Nuclear PSAs before IPE .. ..... 383 11.1.2 ATWS 384 11.1.3 Risk-Based Categorization of NRC Technical and Generic Issues . . . 385 11.1.4 Use of PSA in Decision Making 385 11.1.5 Value-Impact Analysis (VIA) 386 11.1.6 Response to the TMI-2 Accident 386 11.1.7 Special Studies 386 11.1.8 Individual Plant Evaluation PSAs . 392 11.1.9 Risk-Based Regulation . 400 11.1.10 Practical Application of PSA: Utility Experience and NRC Perspective . 402 11.2 PSA of the CANDU (Heavy Water Power Reactor) 404 11.2.1 Reactor Description 404 11.2.2 CANDU-2 PSA 405 11.2.3 CANDU-6 PSA 406 11.2.4 CANDU-9 PSA .407 11.3 Research and Production Reactor PSAs 408 11.3.1 Advanced Test Reactor PSA 408 11.3.2 High Flux Beam Reactor PSA 411 11.3.3 HFIR PSA 414 11.3.4 K-Reactor PSA 416 11.3.5 N-Reactor PSA 422 11.3.6 Omega West Reactor PSA 427 11.4 Chemical Process PSAs 428 11.4.1 Canvey Island 428 11.4.2 PSA of a Butane Storage Facility (Oliveira, 1994) 438 11.4.3 Comparative Applications of HAZOP, Facility Risk Review, and Fault Trees 440 11.4.4 Probabilistic Safety Analysis of an Ammonia Storage Plant 445 11.5 Problems . 449 Chapter 12 Appendix: Software on the Distribution Disk 12.1 ANSPIPE 12.2 BETA 12.3 BNLDATA 12.4 FTAPSUIT Xlll

451 451 452 453 453

12.5 Lambda 1.2.6 UNITSCNV

457 458

Chapter 13 Glossary of Acronyms and Unusual Terms

459

Chapter 14 References 467 14.1 Nuclear Regulatory Commission Reports Identified by NUREG Numbers . . . . 467 14.2 Nuclear Regulatory Commission Contractor Reports Identified by NUREG/CR Numbers 468 14.3 Electric Power Research Institute Reports Identified by NP Number 471 14.4 References by Author and Date . 472 Chapter 15 Answers to Problems 15.1 Chapter 1 15.2 Chapter 2 . 15.3 Chapter 3 15.4 Chapter 4 15.5 Chapter 6 15.6 Chapter 7 15.7 Chapter 8 15.8 Chapter 11

, . . . 493 493 495 . . . 496 500 501 504 504 506

Index

509

xiv

List of Figures*

1.4.2-1 Curve Enveloping Accident Data and a Linear Envelope for a Looser Straight-Line Bound 7 1.4.2-2 Exceedance Probability (accidents 1-6) and composite envelope ,8 1.4.3-1 Fatality Frequency for Man-Caused Events (from WASH-1400) 9 1.4.3-2 Confidence Intervals: CCDF for Latent Cancer Fatalities Internal and External Seismicity 10 1.4.3-3 Latent Cancer Risk at Indian Point site if the Reactor were one of the five types shown 10 1.4.3-4 Early fatality risk if the Indian Point Plant had been at one of these sites 10 1.4.3-5 Risk compared as volumes or masses 11 1.4.3-6 Relative contributions to the Zion and ANO-1 core melt frequencies 12 1,4.4-1 Revealed and risk-benefit relationships .13 2.2-1 Venn diagram of two sets 37 2.2-2 Mincut Explanation by Venn Diagrams 39 2.3-1 Probability of Scores in Craps 40 2.4-1 Venn Diagram of Sets A and B 41 2.5-1 The discrete distribution of probability of crap scores has impressed on it a continuous distribution with quite a different meaning . 43 2.5-2 Conceptual Life-Cycle of a Component 46 2,5-3 Transitions between States 48 2.7-1 ERMA simulation of a low pressure coolant injection system 59 2.7-2 Histogram of probability distribution generated by Monte Carlo simulation 60 2.8-1 Risk worth ratios with respect to core melt for Sequoyah safety systems . . . . . . . . . . . . . 65 2,8-2 Risk worth ratios with respect to core melt for Oconee safety systems 65 2.10-1 Control Rod Pattern 66

3,1.3-1 Example of a Block Flow Diagram 3.1.3-2 Process Flow Diagram 33.1-1 Hydrogen Fluoride Supply System 3.3.1-2 Cooling Tower Water 3.3.4-1 The HAZOP Process 3.4.1-1 Illustrative Cooling Systems 3.4.3-1 Reliability Block Diagram of Figure 3.4.1-1 u

68 69 76 77 88 . . . 98 100

The first number is the chapter number, the second number is the section number and the third number (if present) is the subsection number. The number after the dash is the figure number.

xv

3.4.4-1 Symbols of Fault Tree Analysis 101 3.4,4-2 Sketch of an Internal Combustion Engine 102 3,4.4-3 Fault Tree of Engine . , . 103 3.4.4-4 Example Fault Tree 104 3.4.4-5 Mincut Fault Tree of Figure 3.4.4-4 105 3.4,4-6 Simple injection system .109 3.4.4-7 Failure to Inject Fault Tree 109 3.4.4-8 Boolean Reduction of "Failure to Inject Fault Tree" 109 3.4.4.9 Fault Tree from the Mincut Representation of Figure 3.4.4-8 Fault Tree . . . . 110 3.4.4-10 Success Tree Transformation of Figure 3.4.4-9 Fault Tree . . . . , . , , . 110 3.4.5-1 Event Tree Scenario Depiction 11.1 3.4.5-2 Large LOCA as a Function Event Tree 113 3.4.5-3 Fault Trees at the Nodes of an Event Trees to Determine the Probability . . . . 114 3.4.5-4 Large LOCA as a System Event Tree .115 3.4.5-5 Large LOCA Event Tree in the LESF style 116 3,4.5-6 Containment Event Tree 119 3.5.7-1 Fault Tree diagram of the emergency electric power system 127 3.6-1 The Saphire Main Menu and the Fault Tree Editor Menu 139 3.7-1 Fault Tree of a doubly redundant ECCS 148 3.7-2 Time-sequential testing 149 3.7-3 Staggered testing , 149 4.3-1 Plant Data Processing for PSA 4.4-1 Releases based on plant status 4.4-2 Releases based on cause code 4.4-1 Venn Diagram of Error Cause

163 165 165 , , . ! 67

4.5-1 Phases of Human Reliability Analysis 4.5-2 General incorporation of HRA into the PSA process 4.5-3 Failure vs Problem-Solving Time 4.5-4 HRA Event Tree 4.5-5 HRA Event Tree for Actions Outside the Control Room 4.5-6 Example of Spread in HEPs from IPE for BWRs 5.1-1 Procedures for Analyzing External Events 5.1-2 Comparison of the world frequency-magnitude shape with data from the CMMG 5.1-3 Seismic hazard curves for a hypothetical site 5.1-4 Plan view of nuclear steam supply system 5.1-5 Nodal diagram of a nuclear steam supply system 5.1-6 Large LOCA Seismic Event Tree for a PWR 5.3.1 Fault Tree Identification of Flood-Critical Equipment 5.3-2 Flood data plotted lognorrnally 6.1-1 Sketch of a Pressurized Water Reactor (PWR) 6.1-2 Sketch.of a Boiling Water Reactor (BWR) 6.1-3 The In-Containment Passive Safety Injection System xvi

172 174 180 180 181 183 . 187 . . . . 189 191 19! 191 195 202 204 207 212 215

6.1-4 AP500 Passively Cooled containment ..,,,216 6.1-5 Sketch of the PIUS Principle , 218 6.1-6 SWBR LOCA Response ...219 6.2-1 The Damaged TMI-2 Core ... 221 6.2-2 Schematic of the RBMK-1000 224 6.3-1 Overview of the PSA process 227 6.3-2 Possible PSA Organization Chart 229 6.3-3 Core Damage Master Logic Diagrams for Indian Point 2 and 3 Nuclear Power Stations 233 6.3-4 Organizing the Analysis via Event Tree 236 6.3-3 Relative core melt contributions 238 6.4-1 Emergency Electric Power 238 6.4-2 Procedure for Using FTAPSUIT 240 6.4.-3 Menu for FTAPSUIT 241 6.4-4 FTAPlus Menu 241 6.4-5 Post Processor Menu 241 7.1-1 Increasing Cost of Process Accidents per 4 Year Period 246 7.1 -2 Average Loss by Type of Plant 246 7.1 -3 Average Loss by Loss Mechanism 246 7.1-4 Average Loss by Loss Cause 246 7.1-5 Average Loss by Type of Equipment . 246 7.1-6 Temporary Repair at Flixborough , 250 7.1-7 Common Headers to the MIC Storage Tanks at Bhopal 252 7.1-8 MIC Storage Tank 253 7.2-1 Fertilizers and Uses 264 7,2-2 Uses for Benzene 269 7.2-3 Unsaturated Hydrocarbons from Petroleum 270 7.2-4 Diagram of a Fractional Distillation Column 287 7.2-5 Schematic of a Catalytic Cracking Unit .289 7,3-1 Process Scoping Steps 296 7.3-2 A Detailed PSA 299 7.4-1 Fault Tree for Tank Rupture 304 7.4-2 FTAP Input file 305 7.4-3 FTAP Punch output .305 7.4-4 Appearance of File 305 7.4-5 Edited Output of IMPORTANCE 306 7.4-6 Monte Carlo Calculation of the Chemical Process Tank Rupture . . . . . . . . . . . . . . . . . . 307 8.1-1 Decay Heat from a 3000 MWe Core 310 8,1-2 Total heat evolved from fuel and absorbed by concrete 310 8. l-3a Molten droplets and rivulets begin to flow downward 311 8.1 -3b Formation of a local blockage in colder rod regions 311 8. l-3c Formation of the molten pool 312 8,l-3d Radial and axial growth of themolten pool 312 xvn

8.1-3e Melt migrates to the side and fails the core barrel ,.,, 312 8. l-3f Melt migrates downward into remaining water , 312 8, l-3g Downward progress of coherent molten mass as the below core structure weakens . . . 3 1 2 8. l-3h Failure of support ..312 8. l-3i Two possible modes of accident progression 313 8. l-3j Three possible failure modes 313 8.1-3k Concept of solidified core in concrete after meltdown 313 8.2-1 BMI-2104 suite of codes used in the source term assessment 317 8.2-2 Meltdown model in the MARCH code 318 8.2-3 Complementary cumulative distribution for latent cancer fatalities 320 8.3-1 Lateral diffusion parameter vs distance from the source 322 8.3-2 Vertical diffusion parameter vs distance from the source 322 8.3-3 Correction factors for oy by atmospheric stability class 322 8,3-4 Isotropic Radiation 325 8.3-5 Common Doses from Various Sources 329 9,1-1 Diagram for Hoop Stress ., 334 9.1-2 Viscous Sliding 335 9.1 -3 Diagram for Viscous Flow in a Pipe , . 335 9.1-4 Shock Wave Parameters for a Hemispherical TNT Surface Explosion at Sea level. . . . . 341 9.1-5 Shock Wave Parameters for a Spherical TNT Surface Explosion at Sea .341 9.1-6 Range of LPG Missiles 345 9.1-7 Scaled Fragment Range vs Scaled Force 346 9.2-1 Case Study Refinery and Town 358 9.2-2 Input to Phast 358 9.2-3 Calculated Toxic Plumes on Map . . . . . . . . 360 10,1-1 PSA Assembly Process 376 11.1-1 Summary of BWR and PWR CDFs from IPEs 395 11.1-2 Conditional Containment Failure Probabilities from the IPEs 395 11.2-1 Sketch of the CANDU 404 11.3-1 Omega West Results .428 11.4-1 Map of the Canvey Island/Thurrock Area 430 11.4-2 Alkylation Process 441 11.4-3 Proposed New Chemical Reactor 444 11.4-4 Case Studies of QRA Results . . . 444 12.1-1 Main Screen for ANSPIPE 451 12.1-2 Main Beta Screen 452 ! 2.4-1 Procedure for Using FTAPSUIT 453 12.4-1 Menu for FTAPSUIT .455 12.4-2 FTAPlus Menu 455 12.4-3 Postprocessor Menu 455 12.4-4 Menu for Lambda , 457 ! 2.4-5 Menu for the Units Conversion Program 457

xvm

15,1.2-1 Redraw of Figure 1.4.3-1 15.1,3-1 Comparing by Area 15.2,1-1 Control Rod Pattern 15.3. l-l Slow Melt Fault Tree 15.3.1-2 Melt Fault Tree 15.3,2-1 RED of a Simple Injection System 15.3.5-1 Fault Tree of Emergency Electric Power 15.4.3-1 HRA Tree for Driving to Work 15.5.2-1 The Percolator Scheme 15.5.2-2 Using Residual Heat 15.6.1-1 Bhopal Accident Event Tree 15.6.2-1 Failure to Inject Fault Tree Input 15.7.2-1 A Radiation Fallout Field

xix

493 493 495 497 497 . . . . 497 498 501 503 503 504 504 505

List of Tablesb

1.4,3-1 Illustrative Cutset Listing 9 1.4.3-2 Expected Annual Consequences (risk) from Five LWR Designs if Sited at Indian Point 11 1.4.3-3 Estimated Frequencies of Severe Core Damage 11 1.6-1 Chronology of Federal Emergency Regulations 15 1.6-2 Emergency Action Levels and Responses 17 1.8-1 Some Federal Regulations Governing the Environment 18 1.9-1 List of Highly-Hazardous Chemicals, Toxics, and Reactives (Mandatory) . . . . . . . . . . . . 28 2.1-1 Comparison of Ordinary and Boolean Algebra , . 36 2.5-1 Values of the Inverse Cumulative Chi-Squared Distribution in terms of percentage confidence with M failures . , 47 2.5-2 Mean Variance and Moment-Generating Functions for Several Distributions . . . . . . . . . 49 .2.6-1 Bayes Conjugate Self-Replication 52 2.6-2 Effect of Bayes Conjugation on a Gamma Prior ... 52 2.8-1 Relationships between Importance Measures 64

3.3.1-1 Possible Checklist Main Headings 77 3,3.1-2 Possible Headings and Subheadings 78 3.3.1-3 Simplified Process Hazards Analysis Checklist 79 3.3.1-4 Checklist Analysis of Dock 8 HF Supply . . . 80 3.3.1-5 Checklist of Cooling Tower Chlorination 80 3.3.1-6 Estimated Time for a Checklist 81 3.3.2-1 What-If Analysis of Dock 8 HF Supply System 82 3.3.2-2 What-If Analysis of the Cooling Tower Chlorination System . . . . . . . . . . . . . . 83 3.3.2-3 Estimated Time for a What-If 84 3.3.3-1 Estimated Time for a What-If/Checklist 85 3.3.3-2 What-If/Checklist Analysis of Dock 8 HF Supply System 85 3.3.3-3 What-If/Checklist Analysis of Cooling Tower Chlorination System 85 3.3.4-1 Guide Words for HAZOP 90 3.3.4-2 HAZOP Process Parameters and Deviations 91 3.3.4-3 HAZOP of the Cooling Tower Chlorination System 92 b

The first number is the chapter number, the second number is the section number and the third number (if present) is the subsection number. The number after the dash is the figure number. xx

3,3.4-4 HAZOP of the Dock 8 HF Supply System 93 3.3.4-5 Estimated Time for a HAZOP 93 3.3.5-1 FMEA Consequence Severity Categories 94 3.3.5-2 Partial FMEA for the Cooling Water Chlorination System ,96 3.3.5-3 Partial FMEA for the Dock 8 HF Supply System . . . . . . . . . . . . . . . . . . . . 97 3.3.5-4 Estimated Time for an FMEA 97 3.4.2-1 Failure Modes Effects and Criticality Analysis Applied to System B of Figure 3.4.1-1 99 3.4.4-1 Hypothetical Engine Operating Experience 103 3.4,4-2 Example Format for an Auxiliary Feedwater System Interaction FMEA . . . . . 107 3.4.5-1 Sequence of Events after LOCA 114 3.4.6-1. Summary of Other Methods 120 3.4.6-2 Attributes of GO .... ... 121 3,5.6-1 Generic Beta Factors for Reactor Components 126 3.6-1 Computer Codes for Qualitative Analysis 129 3.6-2 Computer Codes for Quantitative Analysis 131 3.6-3 Computer Codes for Uncertainty Analysis 132 3.6-4 Computer Codes for Dependent-Failure Analysis 133 3.6-5 Code Usage in Utility PSAs 135 3.6-6 Code Usage in PSA Studies 136 3.6-7 The Saphire Suite 137 3.6-8 Applications of the R&R Workstation 1.45 4.1-1 Partial History of Reliability Data Collection 4.1-2 Data Collections 4.1-3 NPDRS Contents 4.1-4 Sample of NUCLARR Comonent Data 4.1-5 NUREG 1150 Nuclear Plant Reliability Data 4.2-1 Internet Web Sites Relevant to Chemical Safety 4.2-3 Some Environmental Internet Addresses 4.3-1 Sources of Data 4.3-2 Contents of Maintenance Reports 4.3-3 Reliability Data Sources for Big Rock Point and Zion PSAs 4.4-1 Studies of Human Error in the CPI Magnitude of the Human Error Problem 4.5-1 HRA Analysis Methods 4.5-2 Requirements for Confusion Matrix 4.5-3 Requirements for Direct Numerical Estimation 4.5-4 Requirements forLER-HEP 4.5-5 Requirements for MAPPS 4.5-6 Requirements for MSF 4.5-7 Requirements for OAT 4.5-8 Requirements for Paired Comparisons 4.5-9 Requirements for SLIM-MAUD xxi

152 154 154 155 156 .158 159 161 . . 162 164 .165 173 175 176 176 . . . . 176 177 177 177 178

4.5-10 Requirements for THERP 178 4.5-11 Sample of NUCLARR Human Error Probability Data 179 4.5-12 Estimated Human Error ,179 4.5-13 Comparison of Human Interaction Evaluations in Utility and NRC PSA Studies . . . . . 182 5-1 Natural and Man-caused Risks 186 5.1-1 Modified Mercali Scale (Wood-Neumann Scale) Perceived Intensity . . . . . . . . . . . . . . . 187 5.1-2 Richter Magnitudes, Energy, Effects and Frequencies 188 5,1-3 Motor-Operated Valve Failure Modes 192 5.1-4 Differences between Seismic and Internal Events Analysis 194 5.1-5 Initiating Events Used in the SSMRP 195 5.2-1 Statistical Evidence of fires in Light Water Nuclear Power Plants* (<May 1978) 197 5.2-2 Distribution of the Frequency of Fires" 198 5.3-1 Turbine Building Flooding in U.S. Nuclear Power Plants 201 5.3-2 Flooding Frequencies for Turbine and Auxiliary Buildings 201 6.1-1 List of PWR Transient Initiating Events .209 6.1 -2 Typical Frontline Systems for PWRs 209 6.1-3 ANO-1 Frontline vs Support and Support vs Support Dependencies 210 6.1-4 List of BWR Transient Initiating Events 213 6.1-5 Typical BWR Frontline Systems , . 214 6.1-6 Attributes for Second-Generation Reactors 214 6.1-7 Comparison Showing Reductions in AP-600 Compared with a Comparable First-Generation Plant 215 6.2-1 Precursors to the TMI-2 Accident ..., . . 222 6.2-2 Summary of the Chernobyl Accident 226 6.3-1 Comparison of Estimated and Actual PSA Resources (person-months) 229 6.3.2 Zion Principal Information Sources 231 6.3.3 Qualitative Categorizations from MIL-STD-882A 232 6.3-4 Sample Preliminary Hazards Analysis , 232 6,3-5 Initiating Event Summaries 234 6.3-6 Inspection Importance Ranking with Health Effects for Indian Point 3 Accident Initiators 235 7.1-1 Safety Enhancement 245 7.1-2 Ammonium Perchlorate Use in Rockets (million Ib/year) 258 7.2-1 Chemical Process Steps 262 7.3-1 Hazard Criteria 293 7.3-2 Objectives for Chemical PSA . . . . . . . . 294 7.3.1-1 A Spread Sheet for Scoping Analysis Data 296 7.3.1-2 Some Toxicology Sources 297 7.3.2-1 Investigations in a Detailed PSA (from CCPS, 1989) 301 7.4-1 Parameters for Figure 7.4-1 304 8.1-1 Melting and Boiling Points of Material 311 8.2-1 Reactor Safety Study Accident Release Categories 315 8.3-1 Units of Radioactivity 327

xxn

8.3-2 Units of Energy Deposition 327 8,3-3 Units of Health Effects , 327 8.3-4 Q Factors for Various Radiation ,,,, 327 8.3-5 Some Maximum Doses from NCRP-91 .329 8.3-6 Codes for Nuclear Accident Consequences 331 9,1-1 Yield. Strength of Some Metals . . . 333 9.1 -2 Temperature Dependent Viscosity of Some Gases and Liquids 336 9.1-3 Gamma for Several Gases 337 9.1-4 Some Heats of Combustion 339 9.1-5 Damage Produced by Blast Overpressure 341 9.3-1 Computer Models on the EPA Disk 37 J 11.1-1 PSA Studies of U.S. Plants Completed before IPE .384 11.1-2 Shutdown CDF (Mid-Loop Operation) and Full Power CDF 390 11.1-3 IPE Submittals .393 11.1-4 IPE Submittals' Containment Types 396 11.1-5 Findings from the IPEs 397 11.1-6 Plants Improvements from IPE from Drouin, 1996 . . , . , . , 399 11.2-1 CANDU-2 PSA Results 405 11.2-2 CANDU-6 PSA Results 406 1J .3-1 ATR Initiating Events 409 J 1.3-2 Quantification of HFBR PSA , 412 11.3-3 HFIR Risk . 416 ! 1.3-4 SRS Methodology 417 ! 1.3-5 SRS Accident Classes .418 11.3-6 Point Estimate CDFs for the K-Reactor .421 11.4-1 Frequency 71000 years of Exceeding Maximum Casualties for Existing Facilities . . . . 437 11.4-2 Risk Reductions and Costs 439 11.4-3 HF Alkylation HAZOP Results 440 11.4-4 Recommendations from FRR of Mining Operation . 442 ] 1.4-5 Frequency (1/y) vs Assumptions 445 11.4-6 Comparison of Some PSA Methods 446 15.3.4-1 Failure Modes Effects Analysis for Valve A in Figure 3.4.4-6 498 15.5.1-1 What-Tf Analysis of Critical Assembly 501 15.6.1-2 Critical Assembly Accident Initiators , . , , 502

xxm

Foreword The last three decades have seen the development of a new science to help us better understand the risk of events about which there is often very little information. The reason there is interest in such a science is that there are a great many societal benefits from activities that involve risk; risk that if properly managed through better understanding can greatly benefit the quality of all life on the planet earth, both plant and animal. That science is quantitative risk assessment, also known by such names as probabilistic risk assessment and probabilistic safety assessment, the latter being the preferred name for this text. Probabilistic safety assessment divides the risk question into three questions "What can go wrong?" "How likely is it?" and "What are the consequences?" Probabilistic safety assessment has had its greatest push in relation to the assessment of risk associated with nuclear power plant operation as documented in the author's previous book. This new book, besides updating and reorganizing the nuclear portions of the previous text, ventures into the safety assessment of chemical facilities, another important industry driver of probabilistic safety assessment methods and applications. As expected, the nuclear sections of this book have much greater scope (breadth and depth) than the chemical sections. This is a direct result of the difference in the experience of the two industries in the development and application of PSA methods. The great appeal of extending the text to the chemical field is that it indicates not only the growth of the discipline, but the contribution to PSA that can come from different industries applying such methods. For example, the chemical field is extremely cost and competitively driven and has been very innovative in coupling safety assessment with plant performance considerations, a factor not nearly as visible in nuclear safety analysis. Other advantages of adding the chemical industry safety assessment practices to this text is the extensive operating experience base involved and the efforts of the chemical safety experts to employ more abbreviated probabilistic safety assessment methods. This book, for the most part, is a stand-alone text. It addresses not only the fundamentals of PSA as a science, but insights on the regulatory framework affecting its development and application. In particular, it provides the basic methods of analysis that can be employed, available databases, an excellent set of examples, software resources, chapter summaries that facilitate comprehension, and problem sets that are very well connected to the theory. While much has been written about probabilistic safety assessment over the last three decades, this is the most comprehensive attempt so far to provide a much needed college level textbook for the education of risk and safety professionals. It also provides a valuable reference for any individual curious enough about the risk and safety sciences to want to become much more informed, B. John Garrick, Ph.D, P.E.

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Preface This book aims at a unified presentation of probabilistic safety assessment as it is applied to the chemical processing and nuclear electrical generation industries. As John Garrick points out in the foreword, probabilistic safety assessment has developed over the latter part of this century to assess and thereby enhance safety in industries that have a remote possibility of affecting many people, PSA's genesis was in the space industry to achieve better equipment reliability. Its application to safety came with the U.S. governments "Plowshare" program for peaceful use of nuclear energy for electric power generation. The electric utility industry was reluctant to adopt this energy source because of the unknown liabilities. The Price-Anderson Act provided the insurance to protect the industry from an unknown risk. A worst case analysis (WASH-740) indicated a large potential hazard with unknown probability of occurrence. There had been small-scale probabilistic risk studies, but the first in-depth study was initiated by the U.S. Atomic Energy Commission in September 1972 and completed by the Nuclear Regulatory Commission (NRC). This was known as the "Reactor Safety Study," (WASH-1400, October 1975) that set the pattern for subsequent PSAs not only nuclear, but chemical and transportation. PSA had it beginnings in nuclear power because of the unknown risk and the large amounts of funds for the investigation. There is a close kinship between the chemical process industry and the nuclear electric power industry. In fact once the physics of nuclear reaction was established the rest is chemistry and heat transfer. The word "reactor" is from chemistry for the location the reaction takes place, A nuclear reactor consists of a vessel in which a nuclear reaction heats water to make steam to drive a turbine !,o generate electricity. Thus the primary components are pipes, valves, pumps heat exchangers, and water purifiers similar to the components found in a chemical plant. Following the success of WASH-1400, PSA was used to analyze the chemical processing of nuclear fuel and waste preparation for disposal. A leader in applying PSA to other parts of the chemical process industry has been the AIChE's Center for Chemical Process Safety. A major difference between PSA for nuclear power and PSA for chemical processing has been the lack of government regulations that require risk analysis for chemical processes. A primary impetuous has been the Occupational Safety and Health Administration's (OSHA) PSM rule that defines the application of PSA to the chemical industry for the protection of the public and workers. In addition, the Environmental Protection Agency (EPA) regulates waste disposal. This book describes the evolution of PSA. WASH-1400 provided the first comprehensive estimate of the risk of two nuclear power plants which were assumed to be generic, hence, taken to represent the industry in the U.S. The NRC, the agency responsible for the regulation of nuclear power in the U.S. used and extended WASH-1400 for regulating the plants and making decision on retrofitting, inspection, maintenance and other purposes. Thus, the legal requirements for a nuclear power plant license drives the use of PSA for this purpose. While not an NRC licensee, the Department of Energy applied PSA to its nuclear power plants and process facilities and adopted many of NRC's safety criteria. Considerations for preparing this book were: xxv

Show the long historical usage of PSA by government and industry for protecting health safety, environment and the infrastructure of civilization. PSA has only been known recently by this term, but its processes have long been practiced. Present risk from its basis in insurance. This is the natural basis that says that risk is the product of probability and consequences. Show the complex iterations between government laws and regulations and the PSA response to not only comply but to protect the process industry. The real impact of the accident at the Three-Mile Island nuclear plant was not radiation, which was within regulations but financial losses to the utility and the acceptance of nuclear electrical power in the United States. The effects of the Bhopal accident were in human life but it also had a profound effect on the chemical industry: financially, and its acceptability and growth. Present the mathematics used in PSA in one chapter to be skipped, studied, or referred to according to the readers needs. Provide the reader with a computer disk containing programs that I have found useful and to provide FTAP and its associated programs. Computer codes that calculate fault trees are either proprietary or expensive or both. FTAP and associated codes are the only code suite that is in the public domain.0 The disk proves them grouped as FTAPSUIT as a "bat" file in association with the FTAPLUS program to aid in formatting. FTAPSUIT is a sophisticated set of programs that finds the cutsets, calculates their probabilities, handles dependencies, and calculates importances and uncertainties. It was written long ago before user-friendly interfaces but this fact may assist understanding and learning. As far as I know, this is the only book that merges nuclear and chemical PSA. Although both processes are similar, nuclear PSA places emphasis on reliability and the probabilistic calculation other than the consequence calculation. Chemical PSA places more emphasis on the consequences than on the probability. Chapter 3 presents methods used by both to determine the reliability of systems and the probability of failure. It begins with OSHA's PSM rule that outlines process for use in analyzing PSA. Qualitative methods are presented before quantitative. The chapter ends by describing computer codes to aid in the calculations and results presentation. Chapter 4 presents data and human factors analysis that are used by both industries. Chapter 5 outlines methods for analyzing the effects of "externalities" on plants. These include earthquake, wind, fire and flood. Chapter 6 describes nuclear reactors, and how they are analyzed to determine the probability of an accident. The only major accidents: Three-Mile Island and Chernobyl are described as to cause and response. Chapter 8 describes how the consequences of such an accident are calculated. Chapter 7 describes the scope of the chemical process industry, major recent accidents that have occurred, including Bhopal. It goes on to describe hazardous chemical processes and how to analyze the probability of an accident. Nuclear reactors and how they are analyzed to determine the probability of an accident; Chapter 9 describes how the consequences of such an accident are calculated by hand and computer codes that are available for more detailed calculations. Chapter 10 describes how the accident probabilities and consequences are c

These codes are provided by Dr. Howard Lambert of LLNL and FTA Associates, 3728 Brunell Dr., Oakland CA 94602. XXVI

assembled for a risk assessment. Chapter 11 describes how PSA is applied in both industries. More examples of nuclear than chemical applications are given because many of the chemical applications are proprietary. Chapter 12 describes codes on the distribution disk. Chapter 13 is an extensive glossary to define acronyms for the reader that is unfamiliar with them and allows me to use them as shorthand for those that are familiar to them. Chapter 14 provides references from which some information was extracted and some references are provided for further study by the reader. Chapter 15 provides answers to the problems that are at the end of some of the chapters. These problems are not so much exercises as providing an extension of the text. My answers are not simply stated but are worked out to show the reasoning . I am a physicist who switched to nuclear engineering for my Ph D. My introduction to PSA was as an original participant in the Reactor Safety Study in 1972. Material for this book was first gathered in 1974 for a workshop on what to expect in WASH-1400 (the results of the Reactor Safety Study). Materials were gathered over the years for EPRI, Savannah River Laboratory, and other workshops, A culmination was in 1988 with "Probabilistic Risk Assessment in the Nuclear Power Industry" with Robert Hall as coauthor. This book updates these materials and adds material on PSA in the chemical process industry. I prepared the material for printing using a word processor.

Ralph Fullwood Brookhaven National Laboratory, retired, 1998.

xxvn


Ac knowledg ments I am greatly indebted to many people over the years who have taught and advised me. To Professor Rasmussen who introduced me to the subject and colleagues on the Reactor Safety Study: Dr. William Vesely, John Kelly, Fred Leverenz, and Abel Garcia, To Dr. Robert Erdman for whom I worked at Science Applications International Corporation and other friends in that organization including Kartik Majumdar, Eugene Hughes Dr. Edward Burns, and Dr. Bryce Johnson, To Professor N. J. McCormick at the University of Washington whose book was an inspiration for this one, At Brookhaven National Laboratory, I wish to acknowledge the support, assistance, discussions and suggestions with Robert Hall (coauthor on the first book), and Drs. Robert Baii, Ali Azarm, Robert Bari, John Boccio, Lewis Chu, John Lehner, Semyon Shteyngart, and Trevor Pratt. Helen Todosow was very helpful for library assistance. I am particularly indebted to Dr. Howard Lambert of Lawrence Livermore Laboratory and FTA Associates for providing the PC computer codes FTAP (fault tree code), POSTPR (post processor), IMPORT (importance calculation), MONTE (Monte Carlo error determination), and supporting documentation and instructions. Dr. Richard Walentowicz provided the EPA CD-ROM disk entitled "Exposure Models Library and Integrated Model Evaluation System" with other reference material. Lester Wittenberg of the Center for Chemical Process Safety, AIChE was particularly helpful in providing a chemical industry perspective and reference material as was Dr. Steven Arendt of JBF Associates, Inc. Drs. David Hesse of Battelle Columbus Laboratories and Vinod Mubayi of Brookhaven National Laboratory were very helpful in providing material on the chemical consequence codes. For the foreword, I would like to thank Dr. John Garrick, who began PSA work in the 1960s and innovated many of the procedures. Lastly, I wish to thank my publisher Butterworth-Heinemann and staff for their patient, accurate and prompt work in preparing the manuscript. Ralph R. Full wood

XXIX


Historical Review

Chapter 1 Protecting the Public Health and Safety

Probabilistic Safety Assessment (PSA) is an analytic method for protecting the public health and safety. The institutional methods are traced from early times to the present to show a progressive understanding of risk, related terms and of methods for anticipating safety concerns before they are manifest as death and injury. Besides presenting common definitions of terms related to safety, mathematical representations of risk are presented for calculating risk. Short-comings of the mathematical forms are discussed as well as differences between calculated risk and public perception of risk. Safety goals for nuclear power are discussed as well as the regulatory bases for nuclear power and chemical processing.

1.1 Historical Review 1.1.1 Beginnings State intervention in man's activities to protect the health of the inhabitants goes back to prehistory. The motivation may not have been altogether altruistic; the king acted to protect his subjects because he regarded them as his property. Public health protection began for disease control. With industrialization, came the need for control of even more hazardous forces and substances. This extended protection became technological in accident analysis and response. Present efforts in controlling risk, such as from nuclear power, are a continuation of this development. Safety, as it relates to public protection from disease, has a history extending to early history. Ruins in the Indus Valley reveal that as early as 400 B.C., building codes and sanitary engineering was in effect. The Egyptians from the middle kingdom (approximately 2000 B.C.) had bathroom and sewage facilities, as did the Incas. The Greeks formulated principles of hygiene and attempted to show a causal relationship between environmental factors and disease. Indeed, the basic text on epidemiology for 2,000 years was "Air, Waters, and Places" from the Hippocratic collection. The Romans perceived a relationship between swamps and malaria and drained many swamps. They also devised dust respirators for workers, built sewage systems, public baths and great aqueducts. Officials were empowered to destroy impure foodstuffs and regulate public baths, brothels and burial grounds. Justinian I of Byzantine, to combat one of the worst plagues in history (532 A.D.), set up quarantine posts and required certificates of health for admission to Constantinople.

Protecting the Public Health and Safety

Health protection is a very old concept that has also been incorporated into state religion. The Biblical books: Leviticus and Numbers established dietary laws, rules of hygiene, precautions against contagious diseases and prohibitions against consanguineous marriages. These rules are similar to those imposed by modern states concerning food preservation, epidemic control, and hereditary diseases. While health care declined after the fall of the Roman Empire, England used the common-law concept of public nuisance to protect the public from flagrant cases of polluting the waters. In France, Germany, and Italy, tanners were prohibited from washing skins in the water supply. London, from 1309, had ordinances regulating cesspools and sewers. The Florentines forbade the sale of meat on Monday that had been slaughtered on Friday. National health legislation came into being in the 19th century primarily in the form of laws that governed the conditions of child labor and eventually prohibited it. In Germany, medical police were organized to make and enforce health and safety regulations. Both France and Germany became committed to the proposition that government had a positive duty to provide for the health, safety and welfare of workers and citizens. The coming of industrialization intensified existing problems and created new ones. With the Clearances in England, came migration of farm labor to the cities as well as improvements in agricultural productivity to support the increasing urban population and consequent increase in communicable diseases. Smallpox was the most widespread disease in the 18th century. Peak years in London occurred between 1723 and 1796, with a periodicity of about five years. Each outbreak took over three thousand lives. In the 1740s, 75 % of London's infants died before the age of five. The diseases of typhus and scarlet fever were also major contributors. Victorian England led the world to better health by actions improving nutrition and working conditions. The Public Health Act of 1848, established Local Boards of Health specifying educational levels of the district health officers and empowering them to enforce sanitation requirements.

1.1.2 industrial Revolution The other effects on safety brought by industrialization resulted from new and more powerful energy sources. Although water and wind power was used in the Middle Ages, these forces were "natural" and believed to be understood. However, the steam engine was something new. The original condensation engine was sub-atmospheric, but with Watt's invention and Carnot's theory, the quest for higher steam pressure and temperature began. The original steam generators were simple pressure vessels that were prone to catastrophic failures and loss of life. Due to better boiler design, tube-fired boilers, and boiler inspections, the incidence of catastrophic failure is now to a rare event (about once every 100,000 vessel-years). In Great Britain in 1866, there were 74 steam boiler explosions causing 77 deaths. This was reduced to 17 explosions and 8 deaths in 1900 as a result of inspections performed by the Manchester Steam User Association. In the United States, the American Society of Mechanical Engineers established the ASME Pressure Vessel Codes with comparable reductions.

Historical Review

The development of steam and later the internal combustion engine made possible transportation by rail, road and air at speeds never before experienced. In all cases, the regulations, inspections, and design standards were imposed after the hazards had been exhibited by many deaths and injuries. Nuclear power has attempted, rather successfully, to anticipate the risks before they occur and avoid them through design, control and regulation. PSA is an essential analytical tool for accomplishing this result.

1,1.3 This Century The discovery of nuclear fission made possible a far more concentrated energy source than ever before. Its hazards were recognized from the beginning, and for the first time, a commitment by government, to safely bring a technology on line without the deadly learning experiences that occurred to safely use earlier technologies. During World War II, experience was acquired in the operation of plutonium production and experimental reactors. Shortly after passage of the Atomic Energy Act of 1948, the Reactor Safeguards Committee was formed (1947) which was to merge with the Industrial Committee on Reactor Location Problems (1951) to become the ACRS (Advisory Committee on Reactor Safeguards). The Atomic Energy Act of 1954 made industrial nuclear power possible, and the first plant began operation at Shippingport, PA, in 1957. The risk posed by a nuclear power plant at this time was unknown, hence the Price-Anderson Act was passed to limit the financial risk. The first report on nuclear power plant accidents, WASH-740, was issued by Brookhaven National Laboratory (1957). The consequences predicted were unacceptable, but it was believed that the probability of such an accident was very small. This report and the technically untenable Maximum Credible Accident method in licensing gave rise, during the 1960s, to probabilistic approaches to siting (Farmer, 1967; Otway and Erdmann, 1970) and to accident analysis (Garrick et al., 1967; Salvatori, 1970; Brunot, 1970; Otway et al., 1970; Crosetti, 1971; and Vesely, 1971). The most ambitious of the pre-Reactor Safety Studies was Mulvihill, 1966, which consisted of a fault tree probability analysis followed by consequence analysis of the postulated accidents at a nuclear power plant.

Reactor Safety Study The Reactor Safety Study (RSS) directed by Professor Norman Rasmussen of MIT may have had its beginnings in a letter from Senator Pastore to James Schlesinger, AEC Chairman, requesting risk information for the Price-Anderson renewal. The RSS study began in September 1972 with Saul Levine, full-time staff director assisted by John Bewick and Thomas Murley (all AEC). A significant development of the study was the use of event trees to link the system fault trees to the accident initiators and the core damage states as described in Chapter 3. This was a response to the difficulties encountered in performing the in-plant analysis by fault trees alone. Nathan Villalva and Winston Little proposed the application of decision trees, which was recognized by Saul Levine as providing the structure needed to link accident sequences to equipment failure. The Reactor Safety Study was the most important development in PSA because it:


* * » * » * * * «

Established a pattern for performing a PSA of a nuclear plant; Provided a basis for comparison; Identified transients and small LOCAs as the major risk contributors, rather than the previous emphasis on a large LOCAs; Showed that the radiological risk of a nuclear power plant is small compared with other societal risks; Originated the event tree for linking initiators, systems, and consequences, and introduced the fault tree to a large audience; Compiled a database; Showed that human error is a major contributor; Showed the impact of test and maintenance; and Showed the importance of common mode interactions.

The work was published as draft WASH-1400 in August 1974 and extensively reviewed. The revised report was published as WASH-1400 (FINAL) in October 1975. Following the release of WASH-1400, the techniques were disseminated by the authors and interpreters through publications, lectures, and workshops. Many organizations set up in-house PSA groups, and the nucleus of the organization that had produced the Reactor Safety Study continued at the NRC.

Critique of the Reactor Safety Study (RSS) WASH-1400 (FINAL), Appendix XI presents comments and responses on the draft report. Some of these resulted in changes that were incorporated in the final report. Only a few critiques of the final report have been published. Two of these are NUREG/CR-0400 (Lewis Report) and Kendall, 1977. Of these, the Lewis Report's comments are the most objective (Leverenz and Erdmann, 1979, provide a review of the Lewis review). Some comments are summarized: 1. Despite its shortcomings, WASH-1400 provides at this time (1978) the most complete single picture of accident probabilities associated with nuclear reactors. The fault tree/event tree approach coupled with an adequate database is the best method available to quantify these probabilities. 2. The Committee is unable to determine whether the absolute probabilities of accident sequences in WASH-1400 are high or low, but it is believed that the error bounds on those estimates are, in general, greatly understated. This is due in part to an inability to quantify common cause failures, and in part to some questionable methodological and statistical procedures. 3. It should be noted that the dispersion model for radioactive material developed in WASH-1400 for reactor sites as a class cannot be applied to individual sites without significant refinement and sensitivity tests, 4. The biological effects models should be updated and improved in the light of new information, 5. After having studied the peer comments about some important classes of initiating events, we remain unconvinced of the WASH-1400 conclusion that they contribute negligibly to the overall risk. Examples include fires, earthquakes, and human accident initiation.

Risk Assessment Objectives

6. It is conceptually impossible to be complete in a mathematical sense in the construction of event trees and fault trees. What matters is the approach to completeness and the ability to demonstrate with reasonable assurance that only small contributions are omitted. This inherent limitation means that any calculation using this methodology is always subject to revision and to doubt as to its completeness. 7. The statistical analysis in WASH-1400 suffers from a spectrum of problems, ranging from lack of data on which to base input distributions to the invention and the use of wrong statistical methods. Even when correct, the analysis is often presented in so murky a way as to be very hard to decipher. 8. For a report of this magnitude, confidence in the correctness of the result can only come from a systematic and deep peer review process. The peer review process of WASH-1400 was defective in many ways and the review was inadequate. 9. Lack of scratability is a major failing of the report, impairing both its usefulness and the quality of possible peer review. These criticisms only are partially addressed in subsequent work.

1.2 Risk Assessment Objectives The assessment of risk with respect to nuclear power plants is intended to achieve the following general objectives: * « * »

Identify initiating events and event sequences that might contribute significantly to risk, Provide realistic quantitative measures of the likelihood of the risk contributors, Provide a realistic evaluation of the potential consequences associated with hypothetical accident sequences, and Provide a reasonable risk-based framework for making decisions regarding nuclear plant design, operation, and siting.

One of the products of a nuclear power plant PSA is a list of plant responses to initiating events (accident starters) and the sequences of events that could follow. By evaluating the significance of the identified risk contributors, it is possible to identify the high-risk accident sequences and take actions to mitigate them. Although the consequences of the high-risk accident sequences may vary from one PSA to another, all PSAs attempt to evaluate realistically, the consequences of hypothetical accident sequences. Depending on the scope of the PSA, these evaluations may include an estimation of the number of latent cancers, the number of immediate fatalities, the probability of core damage, or a number of other consequence measures. When used to identify and evaluate significant risk contributors, as well as to assess the consequences of accident sequences, the PSA provides a comprehensive framework for making many types of decisions regarding reactor design, operation, and siting. These and other applications can be facilitated by the rational evaluation of the risks associated with a particular installation.


1.3 Risk, Hazard, and other Terms This text is concerned with quantified risk. To treat any subject mathematically, precise definitions are necessary for a common understanding. Risk is related to safety, danger, hazard, loss, injury, death, toxicity, and peril but it has two meanings that may cause confusion. The first definition concerns "hazard, peril, and exposure to injury or loss," which suggests an unrealized potential for harm. If the danger becomes real, then it is no longer risk but becomes "injury, loss, or death." The second definition is more explicit: "Risk is the chartce of loss, injury, or death." Chance, likelihood, and probability are all related words for a random process.

1.4 Quantitative Aspects of Risk Risk is a nebulous concept, but when low risk equipment leads to major consequences, the public feels that something is wrong - especially after the media perform their work. Putting risk on a mathematical foundation is a first step in setting a number to risk.

1.4,1 Actuarial or Linear Risk To convert the words of the second definition of risk into mathematics, let "chance" be probability, "loss" be consequences, and : "of be multiplication. Expressed in words, this is: Risk = Probability R - p*C (1.4-1) times Consequences which is expressed by equation 1.4-1, using R for ' risk, p for probability, and C for consequence. A useful example of equation 1.4-1 is insurance, which was invented by tne 15th century Genoese to protect against individual N*R-n*C (1.4-2) catastrophic shipping losses by sharing the risk. To derive the risk R = (n/N}*C (1,4-3) equation, suppose the insurer collects premium R for insuring N ships per year of which n are lost and an award C is paid for each lost ship. The insurance company receives N*R in premiums; it pays out n*C and breaks even (neglecting insurance company expenses) when these are equal (equation 1.4-2). Solving equation 1.4-2 for risk gives equation 1.4-3, As N becomes very large, the ratio, n/N, approaches probability, p (Section 2.3). Thus, R = p * C, as stated in equation 1.4-1. To illustrate, if you are in an age group with 1 % probability of dying per year and the insurance pays $10,000, your annual premium must be at least $100 for the insurance company to break-even without considering the insurance company's expenses. A risk equation for nuclear power may be derived by imagining a world with a very large nuclear power plant population. All plants are identical with the same demography and meteorology. The plants are separated such that one does not affect the other. Each year, n,- plants fail in the ith failure mode, causing a population dose dt. If the effects are additive, the population dose (other risk measures could be used) is linearly proportional to the number failing (Equation 1.4-4), where ct is

Quantitative Aspects of Ris-k

a proportionality constant that is interpreted as the average , [ population dose per plant caused by the ith failure mode. ' ' The total population dose D is the sum over the doses from D = S d = Sc*n M failure modes (equation 1.4-5). The probability of » = i ' i---i n occurrence of the ith failure mode in the limit of large N is > , . ,-, *• 11.4-6, f * The -n,- population t *• dose ^ i * andj o.< = lim (1.4-6) equation per year per plant, ^^ — /y hence the plant risk, is given by equation 1.4-7 which says D M = m that risk is the expected consequence in the same sense that ^ ^ ~ = 23 c,- *P,- *• ' -' an insurance premium is the expected consequence of the awards, M In conclusion, risk is probability times consequences which is /? = S cv*p (I 4-8) the expectation value of the consequences. In analogy to insurance, risk /=i is the premium paid by society for the use of a technology. 1.4.2 Shortcomings of Linear Risk Equation 1.4-7 is unsatisfactory because the risk from a large number of small accidents is the same as from a small number of large accidents if the total number of effects, say fatalities, is the same for each case. It is hypothesized that the perceived risk of a large accident is greater than the equivalent risk from many small accidents because of human nature and the emphasis of the news services on the unusual (50,000 traffic deaths per year is not newsworthy, but a single accident killing 50,000 is very newsworthy). To address this nonlinearity, it has been proposed that the risk equation be modified as shown in equation 1.4-8 where the consequences are raised to the v-power to account for the effects of perception. Unfortunately, a physical basis for the value of v has not been established, but a suggested value is 1.2 (NUREG-0739). If v were set to 1, then risk would be linear and not allow for perception. The perception problem may be avoided if risk is considered to be an ordered pair composed of probability and consequences without a relationship between the members of the pair. Figure 1.4.2-1 illustratively shows points representing the probability and consequence of accidents, associated with an activity plotted as a log-log graph. Encompassing the points Linear Envelope are a smooth curve through the maximum points, and a tangent to this curve that defines at the maximum risk (p*C product). Notice that neither curve bounds the total risk they bound the p, C ordered pair combinations. That is, given p, the curves will indicate the maximum consequence with the curve giving a tighter (less conservative) bound than the straight line. The linear curve has the equation: p*c = k, Fi L4 2 ] where k is the constant risk value. (The slope of the constant s- - - Curve Enveloping A cide nt Da ta and risk curve will be 45 ° if the abscissa and ordinate have equal " Unefrt c f , , envelopef for arLooser btratent-Line size decades.) Bound 1


Although discussion up to this point has treated probability and consequences as precise (1.4-9) CCD = \pdf(x) *dx quantities, there are uncertainties associated with both. It is common practice to present uncertainties as a "bell-shaped" curve called a probability distribution, probability density function (pdf), or just Envelope distribution (Figure 2.5-1). Such bell-shaped curves, however, are not probability but are the rate of change of probability (probability density). Probability is obtained ^ by integrating over portions of the probability density. An | exceedance probability (CCDF - complementary I cumulative distribution function) is the integral from x to | '» (equation 1.4-9), This is the way that WASH-1400 presents most of its results. The next section discusses several ways of presenting PRA results and this method in Consequence(x1) particular. Figure 1.4.2-2 illustrates this type of Fig. 1.4,2-2 Exceedance Probability (accidents 1-6) and composite presentation. Instead of showing the accident (p, C) envelope. Each curve represents thtcombinations as dots, the accidents are presented as probability that the consequences of exceedance plots, i.e., the probability that a consequence the accident will be greater than x will be exceeded. some value xt, As a final nnai comment commem on inadequacies of mathematical representations of risk, those who bear the risk are not necessarily those who receive the benefit. While unequal distribution of risk and benefit may not be fair, it is difficult to redress the inequity,

1,4,3 Presentation of Risk Abstract calculations of risk have meaning only when their meaning is understood by people, Their significance may be communicated quantitatively and qualitatively. 1.4.3.1 Qualitative Results System models, even unquantified, provide valuable insight into the robustness of the plant design. Because of the uncertainties in the data used to quantify the PSA, some people say that information in the cutsets is the most valuable result of a PSA. The cutsets are the groupings of things that must fail for an undesirable event to occur. Such an event could be some degree of core melt or it could be some system failing to perform its design function. Table 1.4.3-1 shows a typical cutset listing, grouped according to the order of combinations of failed components (single, double, triple, etc.) that must fail to cause system failure. For example, if failures A and D ("*" is the symbol for logical "AND"), occur concurrently, the system will fail. Furthermore, paired failures G*H, I*J, etc. will fail the system as will the triple combinations P*R*S, P*R*T, etc. Clearly, singlet components are more important than doublet which are more important than triplet

Quantitative Aspects of Risk

components. Prioritization of test, maintenance and inspection activities may be prioritized Table 1.4.3-1 Illustrative Cutset Listing (letters according to their order in a cutset listing. A represent the probability of system failing. The cutset listing also indicates systems that may be ordering has no significance) taken out for repair when the system is Singlet Doublet Triplet, operating. For example, G may be taken out as long as H is functioning, but if L is taken out, A G*H P*R*S the failure of M, N or O will fail the system, B P*R*T I*J thus giving L a higher importance than G. This ordering by singles, doubles and C I*K U*W*T triples takes added meaning when the failure D L*M V*W*T rates of the active and passive components (Table 1.4,3-1) are included. A doublet has a L*N X*Y*Z failure frequency that is the product of the two L*O x*w*s failure rates; a triplet is the product of three failure rates. Another qualitative result, obtained from quantitative analysis, is the ordering of accident sequences, according to their fractional contribution to the risk. The order of the sequences is insensitive to data uncertainties (unless they are extreme). The uncertainties in the data should be carried through the analysis and sensitivity studies performed. It is important to recognize that results can be useful despite large uncertainties because the order of importance may not be strongly affected by the uncertainties. An important product of the analysis is the framework of engineering logic generated in Total man-caused constructing the models. The numerical estimates of frequencies need only be sufficiently accurate to •fashes total distinguish risk-significant plant features. The patterns, ranges, and relative behavior obtained can be used to develop insights into design and operation - insights that can be gained only from an integrated, consistent approach such as PSA. These insights are applicable to regulation and minimizing regulation impact. Thus, PSA techniques serve as a valuable adjunct to the methods currently used in decision Air crashes affecting persons on the ground making by both industry and government. Although not yet developed to the point where they can be used without caution, they provide a framework of integrated engineering logic that can be used to identify and evaluate critical areas that influence , ~ economics and safety.

Fig. 1.4.3-1 Fatality Frequency for Man-Caused Events (from WASH-1400)

Protecting the Public Health and Safely

1,4.3,2 Quantitative Results Figure 1.4.3-t from WASH-1400 compares the risk of 100 nuclear plants with other man-caused risks. This is a CCDF that gives the frequency per year that accidents will exceed a value on the abscissa. For example, for 100 fatalities, the frequency that 100 nuclear power plants could do this is 1E-4, air crashes to persons on the ground: 1E-2, chlorine releases: l.IE-2, dam failures: 7E-2, explosions: 8E-2, fires: 1.1E-1, air crashes (total): 5E-1, and total mancaused: 9E-1, Some comments regarding Figure 1.4.3-1 are: 1. 2.

3.

4.

CCDF plots are difficult for many people to interpret. Many activities are presented but the benefits of each are not the same. For example, there is no viable alternative to air travel, but there are alternatives to producing electricity with nuclear power plants. A better comparison would be between alternative methods for producing the same quantity. This was not done because the authors of WASH-1400 wanted to relate the risk of national nuclear power usage to risks with which the public is more familiar. CCDFs may be compared if they have the same shape. If not, a line of constant risk may be drawn (Figure 1.4.2-1) and the comparison made by comparing the envelopes of constant risk. Figure 1.4.3-1 does not reflect the uncertainties in the analysis; Figure 1.4.3-2 addresses this deficiency by presenting envelopes at the 5, 50, and 95% confidence levels. Of course, including confidence intervals on all curves, e.g., Figure 1.4.3-1 would be confusing.

10

100 'JE-3 Number of latent fatalities, x'

Fig. 1.4.3-2 Confidence Intervals: CCDF for Latent Cancer Fatalities Internal and External Seismicitv

§• 1E-6 — 2. . 3. 4. 5.

Peachbotton Surry PWR rabaselin Sequoyafi ice t Indian Pant before fix Indian Point after fix

100

10

1000

Latent cancer /y

Fig. 1.4.3-3 Latent Cancer Risk at Indian Point site if the Reactor were one of the five types shown.

5. Palisades 8, Diablo Canyon \ ,

1

\

_Ii__

\\ \1_1_

Fig. 1.4.3-4 Early fatality risk if the

\

Figure 1.4.3-3 is an example from the Indian Point Indian Point Plant had been at one hearings showing an effective use of CCDF. The purpose of of these sites this presentation was to assure that the reactor at the Indian Point site is about as safe as any that could be sited there; hence, comparisons are made of the risk 10

Quantitative Aspects of Risk

Table 1.4.3-2 Expected Annual Consequences (Risk) from Five LWR Designs if Sited at Indian Point

Table 1.4.3-3 Estimated Frequencies of Severe Core Damage

Early Deaths

Early Injuries

Latent Cancers

Damage k$

Reactor

Type

Freq./r-yr

IP after fix 2.2E-4

2.7E-4

1.6E-5

199

Surry

3-loop PWR

6E-5

IP before fix

6.3E-4

9.5E-4

4.4E-5

700

Peach Bottom

BWR (Mark!)

3E-5

Sequoyah

Sorry 6.1E-3 rebaselined

1.5E-2

5.4E-4

9,550

4-loop PWR {ice 4E-5 condenser)

Oconee

2-loop PWR

2E-4

Sequoyah ice condenser

2.7E-3

2.2E-2

1.2E-3

14,800

Calvert Cliffs

Calvert Cliffs

2E-4

Crystal River-3

2-loop PWR

3E-4

1..7E-2 Peach Bottom BWR rebaselined

3.1E-3

1.1E-3

13,500

Biblis

4-loop PWR

4E-5

Indian Point

4-loop PWR

1E-5

Situation

posed by other reactors at the same site. Figure 1.4.3-4 is presented Radiological to show that the Indian Point site is reasonable by comparison with some other sites. This figure illustrates the point that CCDFs cannot be compared if the curves have different shapes. Logarithmic scales are frequently used in presenting risk Radiological results but most of the public do not understand logarithmic scales. occupational Full wood and Erdman, 1983 circumvent this problem by comparing risk as cubes in which linear dimensions are the cube root of the volume/risk. Figure 1.4.3-5 compares the risks associated with nuclear fuel reprocessing, refabrication and waste disposal with non- Fig. 1.4.3-5 Risk compared as nuclear risks. volumes or masses Presenting information as a cumulative integral (CCDF) may be confusing. Tables 1.4.3-2 and 1.4.3-3, corresponding to the preceding figures, present considerably more information in terms of expected effects (probability times consequences). Table 1.4.3-2, also from the Indian Point hearings, compares the PSA-assessed probabilities of severe core damage for various reactors. Perhaps the most readily perceived type of presentation is a "pie" chart of the major contributors as determined in the Zion and Arkansas Nuclear One (ANO)-l) PSAs and presented in Figure 1,4,3-6,

11


1,4.4 Public Perception of Risk

Transients All others ,LOCAs with failure 1% ^ with failure ofLTDHR ofLTDHR Transients with j ' 4% "~~~>eaf removal i ', Loss of o/fI offsite (LTDHR) Inc. 1 \ fe power ,' LOCAs with /! \ power event V 59% / \ fra2ftante •' feitoreof \ transients , 20 * .' safefy \18% injection 28% \

The preceding section shows the rather abstract, mathematical methods used to present the results of PSA, While the "public" is a very diverse group, the majority do not receive information in this fashion but receive it through the news media. It is not the nature of news to attempt a balanced presentation but to emphasize the unusual. To illustrate, the LOCAs with Arkansas Nuc 0 fact that 50,000 people die each year in failure of safety ZION mec traffic accidents, involving a few deaths °" . ., , „ , . . . . , „. . ...,. , 0 Fig. J.4.3-6 Relative contributions to the Zton andANO-J r

at a time, IS not newsworthy. Furthermore

core me[t frequencies. Reprinted

with permission of the

the latency of a hazard greatly affects risk Electric Power Research Institute USA perception. If smoking resulted in immediate death, however unlikely, the public attitude would be greatly changed because the causeeffect relationship would be apparent. There is similarity between the risk of smoking and that of a nuclear power accident in that both result in an increase in the probability of cancer developing with a latency period of about 20 years, yet the hazard of nuclear power is perceived quite differently from that of smoking. Equation 1.4-7 showed that as long as consequences are small enough, that effects are linear, i.e., not so catastrophic as to affect the perpetuation of civilization, the number of injuries or fatalities in either case are the same whether or not there are many small accidents or a few large accidents. But the public, either because of information sources or for more fundamental reasons does not see it this way. Since the public affects government, public perception is a concern. The literature on this subject is so large that it cannot be encompassed in a brief review. NUREG/CR-1930 (1981) is a bibliographical survey of 123 references; Covello, 1981 lists 148 references. Since no risk should be tolerated if it has no benefits, most of the papers address the question "How safe is safe enough," by comparisons with acceptable risks. (In many cases these "acceptable" risks are really "tolerated" risks in that the cost of reduction does not seem to be warranted.) Starr, 1969 approached this by investigating the "revealed preferences exhibited in society as the result of trial and error. (Similar to the "efficient market theory" in the stock market.) Stanconjectured that the risk of death from disease appears to determine a level of acceptable voluntary risk but that society requires a much lower level for involuntary risk. He noted that individuals seem to accept a much higher risk (by about 1000 times) if it is voluntary, e.g., sky-diving or mountain climbing, than if it is imposed, such as electric power or commercial air travel, by a correlating with the perceived benefit. From this study, a "law" of acceptable risk was found concluding that risk acceptability is proportional cube of the benefits. Figure 1.4.4-1 from Starr, 1972 shows these relationships. One aspect of revealed preferences is that these preferences do not necessarily remain constant (Starr et al., 1976). In Starr et al., 1976, it is shown that while nuclear power has the least risk of those activities compared, it also has the least perceived benefit. Clearly the public thinks that }2

Safety Goals

alternative ways of producing ?£~3 electricity have less risk despite risk comparisons of various ways of electric power production such as Inhaber, 1979, Okrent, 1980 or Bolten, 1983. Another approach to public INVOLUNTARY perception of risk is to simply ask the | Electric Power public. This was the approach of Fischoff et al., 1977 in ,f? = Risk B = Benefit Natural Disasters which a survey of the League of 1E-11 0 500 1000 SE3 Women Voters in Eugene, Oregon Average annual benefit/person involved ($) was taken. Later studies covered 40 Fig. 1.4.4-1 Revealed and risk-benefit relationships college students at the University of (from Starr, 1971). Reprinted with permission from. Oregon, 25 Eugene businessmen and Perspectives on Benefit-Risk Decision Making, National Academy of Engineering, U.S.A. 15 national experts in risk analysis. Thomas, 1981 reports a survey of 224 selected Austrians. Cross-comparing the risks of various activities is difficult because of the lack of a common basis of comparison, however Cohen and Lee, 1979 provide such a comparison on the basis of loss of life expectancy. Solomon and Abraham, 1979 used an index of harm in a study of 6 occupational harms - three radiological and three nonradiological to bracket high and low estimates of radiological effects. The index of harm consists of a weighting factor for parametric study: the lost time in an industry and the worker population at risk. The conclusions were that the data are too imprecise for firm conclusions but it is possible for a radiation worker under pessimistic health effects assumptions to have as high index of harm as the other industries compared. To conclude, this sampling of the literature of risk perception, the comments of Covello, 1981 may be summarized. Surveys have been of small specialized groups - generally not representative of the population as a whole. There has been little attempt to analyze the effects of ethnicity, religion, sex, region age, occupation and other variables that may affect risk perception. People respond to surveys with the first thing that comes to mind and tend to stick to this answer. They provide an answer to any question asked even when they have no opinion, do not understand the question or have inconsistent beliefs. Surveys are influenced by the order of questions, speed of response, whether a verbal or numerical response is required and by how the answer is posed. Few studies have examined the relationships between perceptions of technological hazards and behavior which seems to be influenced by several factors such as positive identification with a leader, efficacy of social and action, physical proximity to arenas of social conflict.

1,5 Safety Goals During the 1970s, a number of safety requirements were imposed that required backfitting existing nuclear power plants that increased the costs of new plants. It was believed that codifying

13


a level of safety would stabilize the licensing and possibly aid in the public acceptance of nuclear power. The Three Mile Island-2 accident gave further impetus to establishing safety goals because the requirements of IOCFR100 (accidents must be less than 25 rem whole body or 300 rem thyroid dose to any individual) were not even closely approached. Nevertheless the public response essentially invalided the rule. The NRC, in responding to the President's Commission on the Accident at Three Mile Island, stated that it was "prepared to move forward with an explicit policy statement on safety philosophy and the role of safety-cost tradeoffs in the NRC safety decisions," The objective of the policy statement was to establish goals defining a acceptable level of radiological public accident risk imposed on the public by the operation of nuclear electric power plants. Hearings on both coasts were held and suggestions were solicited. Some of the papers that were published in response to this request were: Mattson et al., 1980; Starr, 1980; Salem et al., 1980; O'Donnell; 1982 and Cox and Baybutt, 1982. The NRC issued a "Discussion Paper on Safety Goals for Nuclear Power Plants" (NUREG-880,1983) with qualitative goals and a suggested a quantitative goal of less than one core melt per 10,000 years. Discussions continued and in August 1986 the formal statement was issued by the NRC (Federal Register 51.162 p30029 - 30033), The two qualitative safety goals are: •

«

"Individual members of the public should be provided a level of protection from the consequences of nuclear power plant operation such that individuals bear no significant additional risk to life and health. "Societal risks to life and health from nuclear power plant operation should be comparable to or less than the risks of generating electricity by viable competing technologies and should not be a significant addition to other societal risks."

The statement goes on to acknowledge the contribution of the Reactor Safety Study (WASH-1400) to risk quantification but points out that safety goals were not the study objectives and that the uncertainties make it unsuitable for such a purpose. After pointing out that the death of any individual is not "acceptable," it states two quantitative objectives: •

•

"The risk to an average individual in the vicinity of a nuclear power plant of prompt fatalities that might result from reactor accidents should not exceed 0.1% of the sum of prompt fatality risks from other accidents to which members of the U.S. population are generally exposed." "The risk to the population in the area near a nuclear power plant of cancer fatalities that might result from nuclear power plant operation should not exceed 0.1 % of the sum of cancer fatality risk resulting from all other causes,"

The fraction 0.1% is chosen to be so low that individuals living near a nuclear plant should have no special concern because of the closeness. Uncertainties in the analysis of risk are not caused by the "quantitative methodology" but are highlighted by it. Uncertainty reduction will be achieved by methodological improvements; mean values should be calculated. As a guideline for regulatory implementation, the following is recommended:

14

Emergency Planning Zones

"...the overall mean frequency of a large release of radioactive materials to the environment should be less than 1 in 1,000,000 years of reactor operation." These safety goals are not meant to supersede any of the present conservative design and operational practices such as, defense in depth, low population zone siting or emergency response capabilities. The goals may be considered as a factor in the licensing decision. Commissioner Asselstine of the USNRC provided an additional view by saying that the nuclear industry has been trying to distance itself from the Chernobyl accident on the basis of containment performance (the Russian plant had no containment structure) and recommended "a mean frequency of containment failure in the event of a severe core damage accident should be less than 1 in 100 severe core damage accidents." Commissioner Asselstine also recommends that the large release criterion of less than once per 1,000,000 reactor years be adopted with clarification as to the meaning of a "large release." Commissioner Bernthal, felt that the statement does not address the question "How safe is safe enough?" or assure the public concerning the Chernobyl accident, while preserving the nuclear power option. A fool-proof containment, while protecting the public would not satisfy this last requirement. He furthermore decries the absence of population density consideration in the 0.1% goals which would allow a plant to be located in "New York's Central Park." Furthermore he points out that the 0.1% incremental societal health risk standard that is adopted is a purely subjective assessment of public acceptance. Date 1970 1975

1978 1979 1980 1981 1983

Table 1.6-1 Chronology of Federal Emergency Regulations Description 10CFR50.34 required a discussion of plans for coping with emergencies. The format and content of onsite emergency plans was given in Reg. Guide 1.101. Offsite emergency planning was required for licensing purposes for a low-zone (EPZ) within a 3 mile radius about the plant. hfUREG-0396 defined two EPZ at radii of 10 miles to provide protection from direct radiation by evacuating or sheltering the public and at 50 miles within which food and water interdiction would protect From this dose pathway. President Carter directs the Federal Emergency Management Administration (FEMA) responsibility of offsste emergency planning. The NRC retained jurisdiction over plant licensing and operation with respect to onsite emergency preparedness. NUREG-0654/FEMA-REP-l and 10CFRSO Appendix E gave bases for both onsite and offsite emergency slanning. It requires joint utility, state and local participation in an annual simulated accident exercise as a condition for an operating license. The NUREG-0654, etc., requirements were modified such that the annual exercise is needed only for operation above 5% power. FEMA relaxed the rule for offsite exercises to every two years. The onsite exercise frequency remains the ;ame.

1,6 Emergency Planning Zones The philosophy of public health protection used by the AEC and pursued ever since, is the use of multiple independent barriers, each a significant shield for the public. The last barrier involves the removal of people from the area over which the radioactive plume is expected to pass, interdiction of food supplies and the use of prophylaxis to reduce the iodine dose. Blood 15


transfusions have also been used to save the lives of people lethally exposed. Emergency planning to protect the public in case of a nuclear power accident is in a much more advanced state than the emergency planning for more likely and potentially more dangerous accidents such as poisonous chemical releases or dam failure because it is required by law. It does present some vexing problems regarding legal responsibilities. The Atomic Energy Act of 1954 made the Federal Government responsible for nuclear power but emergency actions may require the participation of several states and many local jurisdictions. The lack of cooperation from any of these may be used to oppose Federal policy. Table 1.6-1 from Buzelli, 1986 gives a chronology of the Federal regulations, Evacuation in case of a nuclear accident had always been considered a possibility to be considered oa an ad hoc basis much as it is for releases of hazardous material that could affect the public. The Reactor Safety Study (WASH-1400, 1975) showed the possibility of some immediate fatalities,8 and set in motion the regulatory process shown in the table. The TMI-2 accident, during which Governor Thornburg, concerned about the possibility of a hydrogen-bubble explosion, recommended an evacuation, did much to increase the concern for emergency planning. In the aftermath of TMI-2, NUREG-0654 and regulations were promulgated that strongly codified the emergency planning process. NUREG-0654 presents bases for emergency planning and its relationship to the EPZ. Sixteen standards are presented to be used in evaluating the plant's emergency plan. The criteria for emergency response are presented in Table 1.6-2, The nuclear power industry has generally opposed these emergency planning requirements partially on the basis of cost but primarily because of the poor public image it gives these plants by involving the public in the drills not required for any other industry. Reducing the size of the EPZ is much to their liking. The technical basis for the size of the EPZ was WASH-1400 which was a basis for the criteria presented in NUREG-0396. Besides demonstrating an evacuation, TMI-2 also demonstrated that the quantities of radioactive releases used in WASH-1400 were grossly conservative for many isotopes. The industry response was the IDCOR program and the NRC response to a reexamination of the "source terms" is contained in NUREG-0956 (discussed in Section 7.2). Hazzan and Warman, 1986 using these and other sources recommend that the EPZ be reduced to 2 miles as does Kaiser, 1986. Solomon and Kastenburg, 1985 reviewed 4 PSA studies of the Shoreharn plant - one of the most affected plants by emergency planning and concluded that plant features would allow a reduction to 10 miles. In concluding this brief discussion on emergency planning, it may be pointed out that the planning criteria are not dependent on the size of the plant nor on special plant features. For example, a plant could have such a strong containment that nothing could escape, even in the most severe accident, and the EPZ would be the same as it is for any other plant. Another anomaly is that the 50 mile ingestion pathway from the Canadian nuclear power plants reach into the U.S. without the same requirements being applied.

*' Immediate in emergency planning means a death within a year of exposure. Long-term deaths are a different problem because of the indistinguishability of a cancer death initiated by radiation and other causes, e.g.., smoking. The effect of a nuclear accident would be a very small contributor to a large background of other causes.

16

Use of PSA by Government and Industry

Emergency class Unusual event (UE) Alert (A)

Table 1.6-2 Emergency Action Levels and Responses Plant criteria Release of activity None Indication of potential plant degradation Actual or potential Minor degradation of plant safety

Site area emergency (SAE) Actual or likely failure of plant safety General emergency (GE)

Small - within Federal guidelines

Actual or imminent Releases reasonably substantial core degradation expected to exceed Federal loss of containment guidelines possible

Response Notification and information Notification and information, partial activation of Emergency Operations Center (EOC) Activation of EOC, deployment of emergency monitoring and communication teams Recommendations to evacuate/shelter for a 2-mile radius, shelter downwind expected to sectors to five miles

1.7 Use of PSA by Government and Industry Interpreting PSA as any risk assessment using accident probabilities and consequences, government and industry have prepared many examples. These are discussed as: Public Risk, Specialized Analyses, and Performance Improvement. Initially PSAs were used, primarily, to evaluate risk imposed on the public or workers. This includes the use of PSA in licensing and/or review procedures to assure protection of public health and safety. Examples by user are: •

•

• •

•

Department of Defense - requires that a PSA be performed according to MIL-STD-882A for any major activity or undertaking, e.g., analyses of the transportation of nuclear weapons and deactivation of chemical weapons. Environmental Protection Agency - has sponsored work on the risk of chemical manufacture and transportation, the risk of reprocessing nuclear fuel, and the risk of nuclear waste disposal. Department of Transportation - has sponsored work on air, ground, rail, and water transportation, using PSA methods. Department of Energy - has sponsored analyses of its reactors and process facilities, the risks of the breeder reactor, the risk of nuclear material transportation and disposal, and the risks of several fuel cycles. Chemical Industry - has risks comparable to or possibly greater then those of the nuclear power industry, but no risk studies of chemical plants in the U.S. have been published. Great Britain, on the other hand, has been active in this area, e.g., the Canvey Island Study (Section 11.4.1 and Green, 1982).

17


«

Nuclear Regulatory Commission - has been a prime mover in the use of PSA and in requiring its use by applicants. Although the Reactor Safety Study (RSS) originated under the Atomic Energy Commission, it was completed by the NRC. Its initial purpose was to provide information for the, at that time, forthcoming Price-Anderson renewal hearings regarding the risk of commercial nuclear power plants,

1.8 Regulation of Nuclear Power 1.S.1 Regulations The regulations concerning nuclear installations in the United States are governed by the Atomic Energy Act of 1954 as amended, and the Energy Reorganization Act of 1974, as amended (which created the NRC, and the DOE). The NRC administers statutes on the licensing of nuclear installations in the United States. In addition, other applicable statutes are given in Table 1.8-1 Nuclear installations in the United States must be licensed by the NRC, but some Federal government facilities are exempt from licensing such as the Department of Energy. Table 1,8-1 Some Federal Regulations Governing the Environment "Low Level Radioactive Waste Policy Amendments "National Environmental Policy Act of 1969 ••Resource Conservation and Recovery Act (RCRA) Act of 1985 "Administrative Procedure Act of 1976 "Toxic Substances Control Act; Clean Air Act of "Coastal Zone Management Act "Endangered Species Act 1977 "Federal Advisory Committee Act Federal Water "Clean Water Act (CWA) of 1977 ••Uranium Mill Tailings Radiation Control Act of Pollution Control Act "Freedom of Information Act 1978 "Comprehensive Environmental Response, "Government in the Sunshine Act Compensation, and Liability Act (CERCLA) of "National Historic Preservation Act "Privacy Act 1980 "Wild and Scenic Rivers Act ••Federal Facilities Compliance Act of 1990 "West Valley Demonstration Project Act of 1980 "Nuclear Waste Policy Act of 1982

1.8.2 Regulatory Structure The NRC delegates the authority for reactor licensing to its Office of Nuclear Reactor Regulation (NRR). Fuel facility, nuclear waste storage and disposal are delegated to the Office of Nuclear Material Safety and Safeguards (NMSS). In cases where public hearings are required, the decision to license, and the condition of the license, rest with an Atomic Safety and Licensing Board {ASLB). For a construction permit, the ASLB decides all issues; in operating license proceedings, the ASLB decides controversial matters. These decisions are subject to review by an Appeal Board

18

Regulation of Nuclear Power

and the NRC Commissioners. In these cases, the NRC staff cannot communicate directly with the Board and the Commission on the merits of the proceedings until a final Commission decision is rendered. Applications for a license to construct and operate an enrichment facility are handled by NMSS; if public hearings are held on such applications, decisions are subject, to review by the Commission. Thus, in the United States, it is necessary to distinguish between actions, positions and decisions of the NRC staff, the Boards, and those of the Commission itself. Additional support for the licensing activities of NRR and NMSS comes from the Office of Nuclear Regulatory Research and Regional Offices,

1.8.3 Licensing Process The licensing process consists of two steps: construction and operating license that must be completed before fuel loading. Licensing covers radiological safety, environmental protection, and antitrust considerations. Activities not defined as production or utilization of special nuclear material (SNM), use simple one-step, Materials Licenses, for the possession of radioactive materials. Examples are: uranium mills, solution recovery plants, UO2 fabrication plants, interim spent fuel storage, and isotopic separation plants. An applicant for a construction permit files a Preliminary Safety Analysis Report (PSAR) presenting design criteria and preliminary design information, hypothetical accident analyses, safety features, and site data. An Environmental Report (ER) must be submitted to evaluate the environmental impact of the proposed facility, and information must be submitted to the Attorney General and the NRC staff for antitrust review. The application is subjected to an acceptance review to determine whether it contains sufficient information for a detailed review, if insufficient, additional information may be requested. When minimum material is submitted, the application is docketed in the Public Document Room, near the project, and an announcement is published in the Federal Register with appropriate officials being informed. When the PSAR is submitted, a substantive review and inspection of the applicant's quality assurance program, covering design, construction and procurement is conducted. The NRC staff reviews the application for undue risk to the health and safety of the public. If such is found, plant modifications may be requested. Additional information for the review are: demography, site characteristics, engineered safety features, design, fabrication, testing, response to transients, accident consequences, PSA conduct of operations, and quality assurance. The NRC staff and its consultants conduct this review over about two to three years using previous evaluations of other licensed reactors. When the review progresses to the point that the staff concludes that the documentation is acceptable, a Safety Evaluation Report is prepared that represents a summary of the review and evaluation of the application by the staff. The National Environmental Policy Act (NEPA) review is performed concurrently by the staff. After completion, a Draft Environmental Statement (DES) is issued and circulated for review and comments by the appropriate Federal, State and local agencies, individuals and public. After receipt of comments and their resolution, the Final Environmental Statement (FES) is issued.

19


When the final design information and plans for operation are ready, a Final Safety Analysis Report (FSAR) and the operating Environmental Report are submitted. The final design of the facility, and the operational and emergency plans are given in the FSAR. Amendments to the application and reports may be submitted from time to time. Each license for operation of a nuclear reactor contains Technical Specifications (Tech. Specs.) and an Environmental Protection Plan assuring the protection of health and the environment. For an early site permit, the application must describe the number, type, thermal power level, and contain a plan for site restoration if the site preparation activities are performed, but the permit expires without being used. The application must identify physical characteristics that could pose a significant impediment to the development of emergency plans. The issues presented in an early site permit proceeding are mostly environmental, but if they involve significant safety issues, they are reported to the ACRS on the permit application. Certified Standard Designs allow preapproval of the NSSS to reduce the time required for power reactor licensing. Applications for certification of a design must contain a level of detail comparable to that required for a final design approval. Combined Construction Permits and Conditional Operating Licenses streamline the licensing process by referencing a standard design and early permitted site.

1.8.4 Public Participation Public hearings are required at the construction permit stage; the ASLB may grant a public hearing at the operating stage if requested by: the NRC, applicant, or a member of the public. The public hearing is conducted by a three-member Atomic Safety and Licensing Board (Board) appointed from the NRC's Atomic Safety and Licensing Board Panel. The Board is composed of a lawyer (chairman), and two technically-qualified persons. The Safety Evaluation, its supplements and the Final Environmental Statement are offered as evidence by the staff at the public hearing. The hearing may be a combined safety and environmental hearing or separate hearings can take place. If the initial decision regarding NEPA and safety matters is favorable, a construction permit is issued to the applicant by the Director of NRR. The Board's initial decision is, in the case of a reactor license application, subject to review by an Atomic Safety and Licensing Appeal Board.

1.8.5 Advisory Committee on Reactor Safety (ACRS) The ACRS is an independent statutory committee that advises the Commission on reactor safety, and reviews each application for a construction permit or an operating license. It is composed of a maximum of fifteen members appointed by the Commission for terms of four years each. As soon as an application for a construction permit is docketed, copies of the PSAR are provided to the ACRS for assignment to a project subcommittee consisting of four to five members. During the Staff review, the ACRS is kept informed of requests for additional information, meetings and potential design changes. If the plant is a "standard design" and the site appears acceptable, the subcommittee review does not begin until the staff has nearly completed its detailed review. Otherwise, the ACRS subcommittee begins its formal review early in the process. The Staffs Safety 20

Regulation ot Nut KH fo^r,

Evaluation Report and the ACRS subcommittee's report form the basis for ACRS's consideration of a project. The full ACRS meets, publicly, at least once with the staff and applicant and issues a letter report to the Commission and public.

1.8.6 Inspection Construction inspections encompass all safety-related construction activities at the facility site. They consist of observation of work performance, quality assurance, testing, examination, inspection, records and maintenance. Inspection of pre-operational testing and operational readiness verifies the operability of systems, structures and components related to safety and whether the results of such tests demonstrate that the plant is ready for operation as specified in the S AR. It also verifies that the licensee has an operating organization and procedures consistent with the S AR; it verifies whether the tests conducted under both transient and operating conditions are consistent with the SAR. It also verifies that licensee management controls for the test program are consistent with NRC requirements and commitments. Operations phase inspections verify, through direct observation, personnel interviews, and review of facility records and procedures that the licensee's management control system is effective and the facility is being operated safely and in conformance with the regulatory requirements. The NRC inspection program assigns resident inspectors at power reactors that are under construction or already operating. The licensee must give any resident inspector immediate, uninhibited access to the facility. In addition to regular inspections, staff members from several NRC offices investigate any significant incident and determine any hazards. Enforcement involves plant shutdowns, corporation and individual fines, and incarceration.

1.8.7 Decommissioning The regulations require, before a license can be terminated, that the NRC must determine that the licensee's decommissioning activities have been carried out in accordance with the approved decommissioning plan, and the NRC order authorizing decommissioning with a final radiation survey demonstrating that the premises are suitable for release for unrestricted use. The regulations require licensee funding and completion of the decommissioning in a manner that protects public health, safety and environment.

1.8.8 Accident Severity Criteria 10 Code of Federal Regulations (10CFR) part 100 provides reactor siting criteria. It specifies that the fission product release calculated for major hypothetical accidents shall produce a whole

21

S:>rotect:ing the Public Health and Safety

body dose less than 25 rem or thyroid dose less than 300 rem to the public (people outside of the site boundary fence). These criteria are not accepted limits but are intended as reference values.1'

1,8.9 PSA Requirements There are no PSA requirements for licensing the current generation of nuclear power plants.0 Nevertheless PSA (PRA to the NRC) has been a tool for regulatory decisions by the NRC and has been used for compliance demonstration and modification justification by licensees. 10CFR50.54(f) states that the licensee must submit individual plant examinations (IPE) of significant safety issues to justify continuing operation of a reactor facility. The NRC issued Generic Letter stating that utilities with existing PSAs or similar analysis use these results, provided they are updated and certified that they reflect the actual design, operation, maintenance and emergency operations of the plant. The methodologies allow the user to determine dominant accident sequences and to assess the core damage preventive and mitigative capabilities of their plant. The IPEs are needed to confirm the absence of any plant unique vulnerabilities to severe accidents. This is to confirm vulnerabilities, identified by PRAs that were not previously identified by traditional methods. The Generic Letter does not specify methodology or contents of an acceptable PSA. A satisfactory analysis is to be determined by the NRC staff, although NUREG-1560, volume 2 part 4 lists attributes of a quality PSA.

1.9 Regulation of Chemical Processing and Wastes Chemical regulation is primarily concerned with the consequences to the public that may result from chemical releases to the environment. Note there is less concern with the probability than with the consequences of release. The major U. S. environmental laws are as follows.

1,9.1 Environmental Law 1.9.1.1 Clean Air Act (CAA) 42 U.S.C. s/s 7401 et seq. (1970) The Clean Air Act is the comprehensive Federal law that regulates air emissions from area, stationary, and mobile sources. This law authorizes the U.S. Environmental Protection Agency (EPA) to establish National Ambient Air Quality Standards (NAAQS) to protect public health and the environment. The goal of the Act was to set and achieve NAAQS in every state by 1975. This setting of maximum pollutant standards was coupled with directing the states to develop state

h

Author's note - The accident at TMI-1 released radioactivity far below 1QCFR criteria but still the licensee was subject to severe regulatory action and suffered severe financial loss. c

10CFR52 requires a PSA for the next generation of nuclear power plants. 22

Regulation of Chemical Processing and Waste

implementation plans (SIPs) applicable to appropriate industrial sources in the state. The Act was amended in 1977 to set new goals for achieving NAAQS, since many areas of the country had failed to meet the deadlines. The 1990 amendments to the Clean Air Act in large part were intended to meet unaddressed or insufficiently addressed problems such as acid rain, ground level ozone, stratospheric ozone depletion, and air toxics. 1.9.1.2 Clean Water Act (CWA) 33 U.S.C. s/s 121 et seq. (1977) The Clean Water Act is a 1977 amendment to the Federal Water Pollution Control Act of 1972, that set the basic structure for regulating discharges of pollutants to waters of the United States, This law gave the EPA the authority to set effluent standards on an industry-by-industry basis and continued the requirements to set water quality standards for all contaminants in surface waters, The CWA makes it unlawful for any person to discharge any pollutant from a point source into navigable waters unless a permit (NPDES) is obtained under the Act. The 1977 amendments focused on toxic pollutants. In 1987, the CWA was reauthorized and again focused on toxic substances, authorized citizen suit provisions, and funded sewage treatment plants (POTWs) under the Construction Grants Program. The CWA provides for the delegation by EPA of many permitting, administrative, and enforcement aspects, of the law to state governments. In states with the authority to implement CWA programs, EPA still retains oversight responsibilities, 1.9.1.3 Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA or Superfund) 42 U.S.C. s/s 9601 et seq. (1980) CERCLA (pronounced "serk-la") provides a Federal "Superfund" to clean up uncontrolled or abandoned hazardous waste sites as well as accidents, spills, and other emergency releases of pollutants and contaminants into the environment. Through the Act, EPA was given power to seek out those parties responsible for any release and assure their cooperation in the cleanup. EPA cleans up orphan sites when potentially responsible parties (PRPs) cannot be identified or located, or when they fail to act. Through various enforcement tools, EPA obtains private party cleanup through orders, consent decrees, and other small party settlements. EPA also recovers costs from financially viable individuals and companies once a response action has been completed. It is authorized to implement the Act in all 50 states and U.S. territories. Superfund site identification, monitoring, and response activities in states are coordinated through the state environmental protection or waste management agencies. 1.9.1.4 Emergency Planning & Community Right-to-Know Act (EPCRA) 42 U.S.C. 11011 et seq. (1986) This is also known as Title III of SARA, EPCRA was enacted by Congress as the national legislation on community safety. This law was designed to help local communities protect public health, safety, and the environment from chemical hazards. To implement EPCRA, Congress required each state to appoint a State Emergency Response Commission (SERC). The SERCs were 23


required to divide their states into Emergency Planning Districts and to name a Local Emergency Planning Committee (LEPC) for each district. Broad representation by firefighters, health officials, government and media representatives, community groups, industrial facilities, and emergency managers ensures that all necessary elements of the planning process are represented,

1.9.1.5 Endangered Species Act 7 U.S.C. 136; 16 U.S.C. 460 et seq (1973) The Endangered Species Act provides a program for the conservation of threatened and endangered plants and animals and the habitats in which they are found. The U.S. Fish and Wildlife Service (FWS) of the Department of Interior maintains the list of 632 endangered species (326 are plants) and 190 threatened species (78 are plants). Species include birds, insects, fish, reptiles, mammals, crustaceans, flowers, grasses, and trees. Anyone can petition FWS to include a species on this list or to prevent some activity, such as logging, mining, or dam building. The law prohibits any action, administrative or real, that results in a "taking" of a listed species, or adversely affects habitat. Likewise, import, export, interstate, and foreign commerce of listed species are alt prohibited. EPA's decision to register a pesticide is based in part on the risk of adverse effects on endangered species as well as the environmental fate (how a pesticide will affect the habitat). Under FIFRA, EPA can issue emergency suspensions of certain pesticides to cancel, or restrict their use if an endangered species will be adversely affected. Under a new program, EPA, FWS, and USDA are distributing hundreds of county bulletins which include habitat maps, pesticide use limitations, and other actions required to protect listed species. In addition, EPA enforces regulations under various treaties, including the Convention on International Trade in Endangered Species of Wild Fauna and Flora (CITES). The U.S. and 70 other nations have established procedures to regulate the import and export of imperiled species and their habitat. The Fish and Wildlife Service works with U.S. Customs agents to stop the illegal trade of species, including the Black Rhino, African elephants, tropical birds and fish, orchids, and various corals. 1.9.1.6 Federal Insecticide, Fungicide and Rodenticide Act (FIFRA) 7 U.S.C, s/s 135 et seq. (1972) The primary focus of FIFRA provides Federal control of pesticide distribution, sale, and use. EPA was given authority under FIFRA not only to study the consequences of pesticide usage but also to require users (farmers, utility companies, and others) to register when purchasing pesticides. Through later amendments to the law, users also must take examinations for certification as applicators of pesticides. All pesticides used in the U.S. must be registered (licensed) by EPA. Registration assures that pesticides will be properly labeled and that, if used in accordance with specifications, will not cause unreasonable harm to the environment.

24


1.9.1.7 Freedom of Information Act (FOIA) U.S.C. s/s 552 (1966) The Freedom of Information Act provides specifically that "any person" can make requests for government information. Citizens who make requests are not required to identify themselves or explain why they want the information they have requested. The position of Congress in passing FOIA was that the workings of government are "for and by the people" and that the benefits of government information should be made available to everyone. All branches of the Federal government must adhere to the provisions of FOIA with certain restrictions for work in progress (early drafts), enforcement, confidential information, classified documents, and national security information. 1.9.1.8 National Environmental Policy Act (NEPA) 42 U.S.C. s/s 4321 et seq. (1969) The National Environmental Policy Act was one of the first laws written to establish the broad national framework for protecting the environment. NEPA's basic policy is to assure that all branches of government give proper consideration to the environment prior to undertaking any major Federal action which significantly affects the environment. NEPA requirements are invoked when airports, buildings, military complexes, highways, parkland purchases, and other Federal activities are proposed. Environmental Assessments (EAs) and Environmental Impact Statements (EISs) that assess the likelihood of impacts from alternative courses of action, are required from all Federal agencies and are the most visible NEPA requirements. 1.9.1.9 Occupational Safety and Health Act 29 U.S.C. 61 et seq. (1970) Congress passed the Occupational and Safety Health Act to ensure worker and workplace safety. Their goal was to make sure employers provide their workers a place of employment free from recognized hazards to safety and health, such as exposure to toxic chemicals, excessive noise levels, mechanical dangers, heat or cold stress, or unsanitary conditions. In order to establish standards for workplace health and safety, the Act also created the National Institute for Occupational Safety and Health (NIOSH) as the research institution for the Occupational Safety and Health Administration (OSHA). OSHA is a division of the U.S. Department of Labor which oversees the administration of the Act and enforces Federal standards in all 50 states. 1.9.1.10 Pollution Prevention Act 42 U.S.C. 13101 and 13102, s/s 6602 et. seq. (1990) The Pollution Prevention Act focused industry, government, and public attention on reducing the amount of pollution produced through cost-effective changes in production, operation, and raw materials use. Opportunities for source reduction are often not realized because existing regulations, and the industrial resources required for compliance, focus on treatment and disposal. Source reduction is fundamentally different and more desirable than waste management or pollution control. Pollution prevention also includes other practices that increase efficiency in the use of energy, water,

25


or other natural resources, and protect our resource base through conservation. Practices include recycling, source reduction, and sustainable agriculture. 1.9.1.11 Resource Conservation and Recovery Act (RCRA) 42 U.S.C. s/s 321 et secj. (1976) RCRA (pronounced "reck-rah") gave EPA the authority to control hazardous waste from "cradle-to-grave" including generation, transportation, treatment, storage, and disposal of hazardous waste. RCRA also set forth a framework for the management of non-hazardous solid wastes. The 1936 amendments to RCRA enabled EPA to address environmental problems that could result from underground tanks storing petroleum and other hazardous substances. RCRA focuses only on active and future facilities and does not address abandoned or historical sites (see CERCLA). The 1984 Federal Hazardous and Solid Waste Amendments (HSWA, pronounced "hiss-wa") to RCRA requires phasing-out land disposal of hazardous waste. Some of the other mandates of this law include increased enforcement authority for EPA, more stringent hazardous waste management standards, and a comprehensive underground storage tank program. 1.9.1.12 Safe Drinking Water Act (SOWA) 43 U.S.C. s/s 3001 et seq. (1974) The Safe Drinking Water Act protects the quality of drinking water in the U.S. This law focuses on all waters actually or potentially designated for drinking use, whether above or below ground. The Act authorized EPA to establish safe standards of purity and required all owners or operators of public water systems to comply with primary (health-related) standards. State governments, that assume this power from EPA, also encourage attainment of secondary standards (nuisance -related). 1.9.1.13 Superfund Amendments and Reauthorization Act (SARA) 42 U.S.C. 9601 et seq. (1986) The Superfund Amendments and Reauthorization Act of 1986 reauthorized CERCLA to continue cleanup activities around the country. Several site-specific amendments, definitions, clarifications, and technical requirements were added to the legislation, including additional enforcement authorities. Title ni of SARA also authorized the Emergency Planning and Community Right-to-Know Act (EPCRA). 1.9.1.14 Toxic Substances Control Act (TSCA) 15 U.S.C. s/s 2601 et seq. (1976) The Toxic Substances Control Act of 1976 was enacted by Congress to test, regulate, and screen all chemicals produced or imported into the U.S. Many thousands of chemicals and their compounds are developed each year with unknown toxic or dangerous characteristics. To prevent tragic consequences, TSCA requires that any chemical that reaches the consumer market be tested for possible toxic effects prior to commercial manufacture. Any chemical that poses health and 26


environmental hazards is tracked and reported under TSCA. Procedures are authorized for corrective action under TSCA in cases of cleanup of toxic materials contamination. TSCA supplements other Federal statutes, including the Clean Air Act and the Toxic Release Inventory under EPCRA.

1.9.2 Occupational Risk Protection: The PSM Rule The chemical industry is not licensed by the Federal Government. Plants are built to the Uniform Building Code, Fire Protection Code and other applicable codes as needed for insurance purposes. They are subject to EPA regarding effluents, and OSHA for worker safety but there is no watchdog for public safety like the NRC. However OSHA in the PSM Rule (process safety management rule) takes a major step in requiring PSA analysis of operating facilities. The following is a condensation of the PSM Rule. Reference should be made to 29CFR1910.119 for the full text. The PSM Rule provides requirements for preventing or minimizing the consequences of catastrophic releases of toxic, reactive, flammable, or explosive chemicals. These releases may result in toxic, fire or explosion hazards. The section applies to processes involving chemical, in excess of the threshold quantities listed in Table 1.9-1, flammable liquids or gases at one location in excess of 10,000 Ibs, hydrocarbon fuels for workplace consumption, and flammable liquids stored in atmospheric tanks kept below their normal boiling points without refrigeration. It does not apply to: retail facilities, oil or gas well drilling or servicing operations, or normally unoccupied remote facilities,

1.9,2.1 Information Safety Plan Employers shall develop a written action plan that implements employee participation in developing and conducting process hazards analyses and other elements of process safety management. The written process safety information shall be prepared by the employer before conducting process hazard analysis. It shall include information on hazards of the hazardous chemicals used or produced by the process, information pertaining to the technology of the process, and information pertaining to the equipment in the process.

Hazardous Chemical and Process Information Materials information includes: toxicity, permissible exposure limits, physical properties, reactivity, corrosivity, thermal and chemical and hazardous effects of inadvertent mixing of different materials.d Process information consists of: 1) process flow diagrams, 2) process chemistry descriptions, 3) maximum amounts of chemicals, 4) safe ranges for temperatures, pressures, flows or 5) evaluation of the consequences of deviations. li

Note: Material Safety Data Sheets meeting the requirements of 29 CFR 1910.1200(g) may provide this information. They are available from, e.g., website http://hazard.com/. 27


Table 1.9-1 List of Highly-Hazardous Chemicals, Toxics, and Reactives (Mandatory) Chemical

CAS"

JQh

Chemical

CAS"

TQh

Acetaldehyde

75-07-0

2500

Chlorodiethylaluminum (also called Diethylaluminum Chloride)

96-10-6

5000 5000

Acrolein (2-Propenal)

107-02-8

150

l-Chloro-2, 4-Dinitrobenzene

97-00-7

Acrylyi Chloride

814-68-6

250

Chloromethyl Methyl Ether

107-30-2

500

Ally] Chloride

107-05-1

1000

Chloropicrin

76-06-2

500

Aliylamine

107-11-9

1000

Chloropicrin and Methyl Bromide mixture

None

1 500

Alkylaluminums

Varies

5000

Chloropicrin and MethylChloride mixture

None

1500

Ammonia, Anhydrous

7664-41-7

10000

Commune Hydroperoxide

80-15-9

5000

Ammonia solutions (greaterthan 44% ammonia by weight)

7664-41-7

15000

Cyanogen

460-19-5

2500

Ammonium Perchlorate

7790-98-9

7500

Cyanogen Chloride

506-77-4

500

Ammonium Permanganate

7787-36-2

7500

Cyanuric Fluoride

675-14-9

100

Arsine (also called Arsenic Hydride)

7784-42-1

100

Diacetyl Peroxide (concentration greater than 70% )

110-22-5

5000

Bis(ChJoromethyl) Ether

542-88-1

100

Diazomethane

334-88-3

500

Boron Trichloride

10294-34-5

2500

Dibenzoyl Peroxide

94-36-0

7500

Boron Trifluoride

7637-07-2

250

Diborane

19287-45-7

100

Bromine

7726-95-6

1500

Dibutyl Peroxide (Tertiary)

110-05-4

5000

Bromine Chloride

13863-41-7

1500

Dichloro Acetylene

7572-29-4

250

Bromine Pentafluoride

7789-30-2

2500

Dichiorosilane

4l09-%-0

2500

Bromine Trifluoride

7787-71-5

15000

Diethylzinc

557-20-0

10000

3-Bromopropyne (also called Propargyl Bromide)

106-96-7

100

Diisopropyl Peroxydicarbonate

105-64-6

7500

Butyl HydroperoxideCTertiary)

75-91-2

5000

Dilauroyl Peroxide

105-74-8

7500

Butyl Perbenzoate(Tertiary)

614-45-9

7500

Dimethyldichlorosilane

75-78-5

1000

Carbonyl Chloride(see Phosgene)

75-44-5

100

Dimethylhydrazine, 1,1-

57-14-7

1000

Carbonyl Fluoride

353-50-4

2500

Dimethylamine, Anhydrous

124-40-3

2500

Cellulose Nitrate (concentration greaterthan 12.6% nitrogen

9004-70-0

2500

2,4-Dinitroaniline

974)2-9

5000

Chlorine

7782-50-5

1500

Ethyl Nitrite

109-95-5

5000

Chlorine Dioxide

10049-04-4

1000

Ethyl Methyl Ketone Peroxide (also Methyl Ethyl KetonePeroxide; concentration greater than 60%)

1338-23-4

5000

Chlorine Pentrafluoride

13637-63-3

1000

Ethylamine

75-04-7

7500

Chlorine Trifluoride

7790-91-2

1000

Ethylene Fluorohydrin

371-62-0

100

28

Regulation of Chemical Processing and Waste Table 1 .9- 1 List of Highly-Hazardous Chemicals, Toxics, and Reactives (Mandatory continued) Chemical

CAS"

TQ"

Chemical

CAS"

TQh

Ethylene Oxide

75-21-8

5000

Methyl Ethyl Ketone Peroxide (concentration greater than 60%)

1338-23-4

5000

Ethyleneimine

151-56-4

1000

Methyl Fluoroacetate

453-18-9

JOO 100

Fluorine

7782-41-4

1000

Methyl Fiuorosulfate

421-20-5

Formaldehyde (Formalin)

50-00-0

1000

Methyl Hydrazine

60-34-4

100

Furan

1 10-00-9

500

Methyl Iodide

74-88-4

7500

Hexafluoroacetone

684-16-2

5000

Methyl Isocyanate

624-83 9

250

Hydrochloric Acid, Anhydrous

7647-01-0

5000

Methyl Mercaptan

74-93-!

5000

Hydrofluoric Acid, Anhydrous

7664-39-3

1000

Methyl Vinyl Ketone

79-84-4

100

Hydrogen Bromide

10035-10-6

5000

Methy Itrich lorosi lane

75-79-6

500

Hydrogen Chloride

7647-01-0

5000

Nickel Carbonly (Nickel Tetracarbonyl)

13461-39-3

150

Hydrogen Cyanide, Anhydrous

74-90-8

1000

Nitric Acid (94.5% by weight or greater)

7697-37-2

500

Hydrogen Fluoride

7664-39-3

1000

Nitric Oxide

10102-43-9

250

Hydrogen Peroxide (52% by weight or greater)

7722-84-1

7500

Nitroaniline (para Nitroaniline

100-01-6

5000

Hydrogen Selenide

7783-07-5

150

Nitrogen Dioxide

10102-44-0

250

Hydrogen Sulfide

7783-06-4

1500

Nitrogen Oxides (NO; NO2;

10102-44-0

250

NA; NA) Hydroxylamine

7803-49-8

2500

Nitrogen Tetroxide (also called Nitrogen Peroxide)

10544-72-6

250

Iron, Pentacarbonyl

13463-40-6

250

Nitrogen Tri fluoride

7783-54-2

5000

Isopropytamine

75-31-0

5000

Nitrogen Trioxide

10544-73-7

250

Keiene

463-51-4

100

Oleum (65% to 80% by weight; also called Fuming Sulfuric Acid)

8014-94-7

1000

Methacrylaldehyde

78-85-3

1000

Osmium Tetroxide

20816-12-0

100

Methacryloyl Chloride

920-46-7

150

Oxygen Difluoride (Fluorine Monoxide)

7783-41-7

100

Methacryloyloxyethyl Isocyanate

30674-80-7

100

Ozone

30028-15-6

KM)

Methyl Acrylonitrile

126-98-7

250

Pentaborane

19624-22-7

100

Methylamine. Anhydrous

74-89-5

3000

Peracctic Acid (concentration greater than 60% Acetic Acid; also called Peroxyacetic Acid)

79-21-0

1000

Methyl Bromide

74-83-9

2500

Nitromethane

75-52-5

2500

Methyl Chloride

74-87-3

15000

Perchloric Acid (concentration greater than 60% by weight)

7601-90-3

5000

Methyl Chloroformate

79-22-1

500

Perch loromethyl Mercaptan

594.42-3

150

29

Protecting the Public Health and Safety Table 1 .9-1 List of Highly-Hazardous Chemicals, Toxics, and Reactives (Mandatory continued) Chemical

CAS"

TQh

Chemical

CAS"

TQ"

Perchloryl Fluoride

7616-94-6

5000

Sulfur Pentafluoride

5714-22-7

250

Peroxyacelic Acid (concentration greater than 60% Acetic Acid;also called PeraceticAcid)

79-21-0

1000

Sulfur Tetrafluoride

7783-60-0

250

Phosgene (also called Carbonyl Chloride)

75-44-5

100

Sulfur Trioxide (also called Sulfuric Anhydride)

7446,11-9

1000

Phosphine (HydrogenPhosphide)

7803-51-2

100

Sulfuric Anhydride (also called Sulfur Trioxide)

7446-11-9

1000

Phosphorus Oxychloride (also called Phosphoryl Chloride)

10025-87-3

1000

Tellurium Hexafluoride

7783-80-4

250

Phosphorus Trichloride

7719-12-2

1000

Tetrafluoroethylene

11 6-J 4-3

5000

Phosphoryl Chloride (also called Phosphorus Oxychloride)

10025-87-3

1000

Tetrafluorohydrazine

10036-47-2

5000

Propargyl Bromide

106-96-7

100

Tetramethyl Lead

75-74-1

1000

Propyl Nitrate

627-3-4

2500

Thionyl Chloride

7719-09-7

250

Sarin

107-44-8

100

Trichloro (chloromethyl) Silane

1558-25-4

100

Selenium Hexafluoride

7783-79-1

1000

Trichloro (dichlorophenyl) Silane

27137-85-5

2500

Slibine (Antimony Hydride)

7803-52-3

500

Trichlorosilane

10025-78-2

5000

7446-09-5 1000 Trifluorochloroethylene 10000 79-38-9 Sulfur Dioxide (liquid) a CAS is- Chemical Abstract Service, Internet: http/Ainfo.cas.org, part of the American Chemical Society, 1 !*?5 tfith Street, N W , Washington DC, 20036, Internet: http:\\www.acs.org. h TO "K Threshold Quantity in pounds

Trade secrets may be used in developing the information for the process hazard analysis emergency planning and responses, and compliance audits. Materials that are developed involving trade secrets may be treated as proprietary and may require signed statements for their protection. Equipment information includes: 1) materials of construction, 2) piping and instrument diagrams (P&ID's), 3) electrical, 4) relief system design and design basis, 5) ventilation system design, 6) design codes and standards, 7) material and energy balances, and 8) safety systems (e.g., Interlocks, detection or suppression systems).

1.9.2.2 Process Hazard Analysis An initial process hazard analysis (PrHA) is performed on the processes, appropriate to the complexity to identify, evaluate and control the hazards. Employers determine the priority for conducting process hazard analyses based on a rationale which includes such considerations as extent of the process hazards, number of potentially affected employees, age of the process, and operating history of the process. The process hazard analysis is conducted as soon as possible to scope out the work.

30


PrHA Team A process hazard analysis team includes one or more employees that are process experts and one or more that are process hazard experts in the methodology being used. The employer establishes a system to promptly address the team's results, timely resolve recommendations, schedule completion, and communicate the activities to affected personnel. Every five years after the completion of the initial process hazard analysis, it is equivalently updated and revalidated. Employers retain the required process hazards analyses for the life of the process.

1.9.2.3 Safe Operation Operating Procedures The employer is responsible for developing and implementing written operating procedures that provide clear instructions for safely conducting activities involved in each covered process consistent with the process safety information by addressing: requirements, responsibilities, and procedures for: » Initial startup * Normal operations * Temporary operations * Emergency shutdown * Emergency operations » Normal shutdown * Startup following a process modification or after an emergency shutdown

Operating Limits * *

Consequences of deviations Avoidance of deviations

Safety and Health Considerations * * » * «

Process chemicals and their hazards Precautions: engineering controls, administrative controls, and protective equipment Exposure mitigation Inventory control Special hazards

Safety Systems and Functions » * »

Accessibility of operating procedures Currency of operating procedures - annual employer certification of accuracy Safe work practices for hazards control: lockout/tagout, confined space entry, procedures for opening process boundaries and entrance control for maintenance

Training 31


Initial training: All employees involved in operating a process are trained in a process overview and in the operating procedures. The training includes emphasis on the specific safety and health hazards under all conditions. In lieu of initial training for employees already involved in operating a process, an employer may certify, in writing, that the employee has the required knowledge, skills, and abilities to safely carry out the duties and responsibilities as specified in the operating procedures. Refresher training at least every three years, to each employee involved in operating a process to assure understanding and adherence to current operating procedures. Training for process maintenance employees are trained by the employer in maintaining the integrity of process equipment. This training includes an overview of the process, its hazards and the procedures for safe operation. Documentation records that each employee involved in operating a process has received and understood the training required by this paragraph. The employer prepares a record which contains the identity of the employee, the date of training, and the means used to verify that the employee understood the training.

Inspection and Testing Inspections and tests are performed on the process equipment following recognized and accepted engineering practices. The inspection and test frequency is consistent with manufacturers' recommendations, good engineering practices, and prior operating experience. The inspections and tests are documented to include the date, the name of the responsible person, identification of the equipment, a description of the inspection or test and the results. Equipment deficiencies that are outside acceptable limits (defined by the process safety information) are corrected before further use or in a safe and timely manner.

Quality Assurance In the construction of new plants and equipment, the employer is responsible that the equipment is suitable for the process application. Checks and inspections are performed to assure that equipment is installed properly, and consistent with design specifications and the manufacturer's instructions. Maintenance materials, instructions, spare parts and equipment will be available.

Hot Work Permit The employer issues a hot work permit for hot work operations conducted on or near a covered process. The permit documents that the fire prevention and protection requirements in 29 CFR 1910,252(a) have been implemented prior to beginning the hot work operations; it indicates the date(s) authorized for hot work; and identifies the object on which hot work is performed. The permit is kept on file until completion of the hot work operations.

Management of Change The employer manages changes (except for "replacements in kind") with written procedures for changes in process chemicals, technology, equipment, procedures, and facilities. The procedures assure the following before any change: 32


« * * « » * » *

The technical basis for the proposed change, Impact of change on safety and health, Modifications to operating procedures, Time required, Authorization requirements for the proposed change, Notification of affected employees, Training needed prior to start-up of the process involving the change, and Updating process safety information and operating procedures.

Incident Investigation The employer investigates incidents that result in, or could result in, a catastrophic release of highly hazardous chemicals. An incident investigation is initiated as soon as possible, but before 48 hours following the incident. An incident investigation team is established to consist of one or more experts in the process involved, and accident investigation. The report prepared at the conclusion of the investigation includes at a minimum: * Date of incident, * Date investigation began, * Description of the incident, * Contributing factors, * Recommendations resulting from the investigation, * Resolution the report findings and recommendations, * Documentation of the resolutions and corrective actions, * Report review by all affected personnel, and * Incident report retention for five years.

Emergency Planning and Response An emergency action plan is established and implemented for the entire plant in accordance with the provisions of 29 CFR 1910.38(a) and may be subject to the hazardous waste and emergency response provisions contained in 29 CFR 1910.120 (a), (p) and (q).

Compliance Audits Employers certify compliance with 29CFR1910.119 every three years. The compliance audit is conducted by one or more persons knowledgeable in the process. A report of the audit findings is prepared. The employer documents the response to each of the findings and their correction. The two most recent compliance audits are retained.

1.10 Summary This chapter provided a common basis for understanding the assigning of numerical values to "risk." in the context of probability as the behavior of an ensemble of plants. Predictions of short-term behavior are subject to statistical fluctuations and may be very misleading. Qualitative 33


goals may be established; quantitative safety goals, while more precise, do not enhance the public's understanding of risk choices. Many examples were given of how PSAs results may be presented. Critiques of past PSA were presented with the view of addressing these criticisms and improving upon them in the future. An overview of U.S. regulations that govern radiological and chemical materials to protect the public was given. The chapter concluded with the PSM rule that provides guidelines for safe operation especially of chemical process facilities.

1.11 Problems 1. A certain insurance company requires a 30% overhead on the premiums. If the payment to your beneficiary is $ 100,000 and you pay $ 1,500/yr in premiums, what is your probability of dying in the year? 2. What is the mean frequency of deaths from nuclear power presented by the distribution from WASH-1400 presented in Figure 1.4.3-1? 3. Few people understand graphs plotted logarithmically, (a) Devise a method for compressing widely varying data into a convenient size - like a logarithm does, but more familiar, (b) Apply your method to the Zion data in Figure 1.4.3-6. 4. 10CFR50 Appendix I gives the value of a person-rem as $1,000. The report Biological Effects of Ionizing Radiation (BEIR, 1972) assesses about 10,000 person-rem per death (statistically not exposed to an individual), (a) Given this information, what is the cost of a death from radiation? (b) At Pickett's charge at Gettysburg, approximately 30,000 soldiers died in 30 minutes. What is the expenditure rate per minute if the same life equivalence were used? 5. It has been traditional to subject workers to higher risks than the public, (a) Write a short discussion of the equities of this practice with consideration for the fact the worker may leave employment that imposed a long term risk, (b) The Nevada Test Site has been selected as a possible location for a high level waste repository. For purposes of the risk assessment, the workers in the repository will be treated as workers with subsequent higher allowable risk. There are many other workers at NTS. Discuss whether these should be treated as workers or public, (c) If they are treated as workers in one calculation and public in the other where is the logic in this? 6. Discuss why the EPZ should be independent of plant size, safety features, demography and meteorology. 7. The death rate by automobile is about 1/10 million passenger miles. At TMI-2 Governor Thornburg recommended that everyone susceptible to radiation within a 5 mile radius to evacuate. Assume that 25,000 people evacuate and the distance each traveles is 20 miles, compare the risk of evacuation with the risk of not evacuating, assuming their exposure is 0.5 mrem-person/hr and they evacuate for two days. 8. The government is charged by the Constitution with a responsibility for the public welfare, (a) Discuss the government's responsibility in controlling the risks in society, (b) Tobacco is not subject to the Delaney Amendment that bans material that can be demonstrated to cause cancer in animals regardless of the quantity of material used in the tests. Why aren't all materials subject to the same rules?

34

Chapter 2 Mathematics for Probabilistic Safety

Probabilistic safety is concerned with evaluating harmful effects of an artificial construct on man. This construct may be called an airplane, plant, facility, or system depending on the degree of its complexity." Whatever, it is made of components that must work together, as designed, for the system to accomplish its intended function (to work). A logical system model consists of the important components of a system and the effects that component failure has on the system operability. This model treats each components as either working or not working,1* hence, the state of the system may be represented by a logical equation composed of the states of the components. This, itself, is valuable information but it also may be used to calculate the probability of system failure by replacing each components Boolean state with the probability that that component will fail. A system's risk is the product of its failure probability and the consequences of failure. Hence, the subjects of this chapter are logic modeling and probabilities. Logic modeling uses the algebra of two-state variables called Boolean algebra. Other subjects are: meanings of probability, combining probabilities, calculating failure rates from inspection and incident data by classical and Bayes statistics, treating of uncertainties as distributed variables, calculating confidence intervals, and the importance of components to system operability.

2.1 Boolean Algebra Sfafe Vector It is convenient to consider the operability of a system as a function of its components f-f(crc2,...,cn). If acomponents operability is identified as "1" for operating and "0" for failed, the status of the components at any time may be represented by a system state vector: iff = (1, 1, I, 0, 0) meaning that components 1, 2, and 3 are operating and components 4 and 5 have failed. Requirements for system operability may be represented by a matrix 101 that has Is where components are required and Os where they are non-essential; the result is: cj> = I0li|jr, where the rules

a

The term "system" is used in this book to mean an aggregate of components; the term "component" refers to an entity that is considered as a unit and not decomposed for analysis, h

Degraded states (partially nonworking) can be in a model by defining a discrete degrading state and considering the component to be either in that state or not.

35

Mathematics for Probabilistic Safety

of matrix multiplication apply. The presence of a 1 in the (f> vector indicates an essential condition; This matrix approach is valuable for the concept that the configuration of a plant at any time is represented by a vector whose elements represent the status of the components by a 1 for operable and a 0 for non-operable. A more refined and developed method is Boolean algebra.

Table 2.1-1 Comparison of Ordinary and Boolean Algebra Ordinary Algebra Boolean Algebra Property Commutative A+B = B+A Same A*B = B*A Associative A+(B+C) = Same (A+B)+C A*(B*C) = (A*B)*C Distributive A*(B+C) = Same A*B+A*C A*A = A Idempotency NA A+A = A NA A*A=A~A2 Completeness A+A-1 A+A = 1 A+1=A4-I Unity A+l = 1 A*l = 1 A*1=A 2 A*(A+B) = A +A*B Absorption A*(A+B) = A A+(A*B) = A*(1+B) A+(A*B) = A NA de Morgan's A*B=A+B A+B=A*B theorem Useful A+(A*B)A+(A*B)= A+B relationships A+B~A*B A*(A + B) = A*B A*(A+B) = B+A*(B-A)

Boolean Algebra Boolean Algebra is the algebra of two-state variables invented by George Boole to provide a mathematical structure to logical reasoning. Consider an equation C = A+B in which the variables are not continuous but may only have two values "0" or "' I." Logically, something OR nothing is something; e.g., if A = 1, B = 0 then C = 1 (1 = 1+0). If you have both: A = / and B = /, the requirement is over satisfied and C = / ( l = l+l)as before. It may seem strange that 1 + 1 = 1 but that is the meaning of logic and that is the way Boolean algebra works. The AND condition requires both, represented as C = A *B, If you have A but do not have B then the requirement is not satisfied so C = 1 *0 = 0. Table 2.1-1 compares the ordinary algebra of continuous variables with the Boolean algebra of Is and Os. This table uses the symbols "*" and "+" for the operations of "intersection" (AND) and "union" (OR) which mathematicians represent by "n" and "u" respectively. The symbols "*" and "+" which are the symbols of multiplication and addition, are used because of the similarity of their use to AND and OR in logic. In the table, the rules of commutation, association and distribution are the same for both algebras. Idempotency, unique, to Boolean algebra, relates to redundancy. Having "A" and "A" is the same as only having "A"; "A" or "A" is superfluous and equals "A." Complementation is introduced in the next rule. The universe is represented by "1". Completeness includes everything in this world and not in this world, hence A +A = 1 where not A is: A = 1 -A which is the meaning of complementation. With this understanding, it is impossible to be both A and not A. Similarly A or not A is complete (the universe). Under unity, A is included in the universe (1) so A+1 = 1. For this

Venn Diagrams and Mincuts

reason A*l =1. Absorption follows from previous rules; de Morgan's theorem corresponds to the rules of double negatives in English. The last relationships may be derived from previous. Systems may be modeled using Boolean algebra with twostate representation of component operability. Systems are not usually modeled as equations is not usually done because of preference by engineers for the more schematic methods that are presented in the next chapter.

2,2 Venn Diagram and Mincuts Venn Diagram

A*B A*B A*B A*B" A Venn Diagram is a graphical depiction of logic. It relates pig 2.2-1 Venn diagram of two the universal set ("1") to a system's status represented by "sets.0 Set sets. Upper figure: set A and set B theory is a branch of mathematics with its own symbols and separated but in a universe language. For PSA, the graphical procedure known as a Venn (background) Lower figure: sets A .. .,, , , , and B partially merged diagram serves to illustrate the method. Consider two sets A and B (upper Figure 2.2-1). The two sets are isolated and unrelated. They have no intersection (AND), but the union (OR) operation includes the two circles, fn the lower operation, union is the two circles (A+B the fact that they overlap does not matter). The (2.2-1) left partial moon (1) is A+B; the right partial A +B = (A *B) +(A *B) +(A (A+B)=A+B~(A*B) (2.2-2) moon (3) is A *B . The common lens (2) is A *B . These are depictions of equation 2.2-1, are equivalent to equation 2.2-2 by using complementation and multiplication. Shannon's Method for Expressing Boolean Functions"

Shannon's method,6 expands a Boolean function of n variables in minterms consisting of all combinations of occurrences and non-occurrences of the events of interest. Consider a function of n Boolean variables: f(X,, X2>... Xn) which may be expanded about X, as shown in Equation 2,2-3 where /f/, X2,.,., XJ where 1 replaces J,. This says that a function of Boolean variables equals the function with a variable set to 1 plus the product of NOT the variable times the function with the variable set to 0. By extending Equation 2.2-3, a Boolean function may be expanded about all of its

c

A set is a collection of related elements.

d

This material was adapted from NUREG-0492.

e

Claude Shannon won the Nobel Prize for relating the maximum information transfer to bandwidth using entropy. 37


arguments. For example, Equation 2.2_ 4 is an expansion about X, and X, It AXrX2,...,XnMx^l,x2,.,XjMx^ W^W should be noted that the variables ^V^-.^VÛ.V^)] + multiplying the function on the right are 3 *X2*J(\,otX3,...,XH)] the state variables (minterms) for all +V^ */(0,1 ,X3 xn)], + possible combinations of the function Xl*X2*ftQ,Q,X3,--,Xf)l that mirrors the state configuration. (X*Y)+(X*Z)+(Y*Z) = [X*Y*Z*f(\,\,l)\ This process is continued for all +[X*y*z*;AiÔ)MX*r*z*/li,o,0] variables. The complete expansion has 2" HpJ*Z*mU)HX*j*Z*/(0,l,0)t +IX minterms consisting of all possible combini?^?'0;!)yx*^Z^0'?t0)l f A C / ( l , l , l ) = ( l * l ) +( 0 * l ) + ( l * 0 ) - - l aliens of occurrences and nonoccurrences of V} io)=(i*i)+(0*0)+n *l) I the X variables. Î,0,l) = (l*0)+(0*l)+(0*l) = 0 Each minterm expansion is disjoint' #,0,OJ=-&d! (2.2-6b) ( J2-6c> ££' (2.2-6f)

X{*X'2*j(\,Q,Xv...,Xn),

(22~6gf

Xt*X2*J(Q,lJCy...,XH)

and

y(0,0,0)=(0*OHl*0)+(0*0)=0

(2,2-3) (2.2-4)

(2.2-5)

/9->A.,|

Y^Y2*/(QAXy-,xn), x,xj(l,\,Xy,Xn) are disjoint.8 Another reason for representing a Boolean function in minterms is their uniqueness. Such an expansion, then, provides a general technique for determining the equality of two Boolean expressions by identical minterms. Shannon's expansion is demonstrated for two, 3-variable functions in Equation 2.2-5 which equates the first function to its expansion. Equations 2.2-6a-g evaluate the functions for all combinations of values for X, Y, and Z. Equation 2.2-7 equates the second function to its expansion, and equations 2.2-8a-g evaluate the functions for all combinations of values for X, Y, and Z. Notice that equations 2.2-6a-g produce the same results as equations 2.2-8a-g. Furthermore, only those equations that result in "I" have relevance. This means that Boolean equation 2.2-5 is the {x*io+(l*Z) = [X*y*z*/CUl)]+ (2.2-7) same as 2.2-7 and the third term in equation 2.2-5 is [x*F*Z*-y(l 10)]+[X*?*Z*'/(l 0 0] superfluous. Figure 2.2-2 interprets these equations as +[X*F*Z*/(0,] ,1)] •t-[X*K*Z*/(0,l,0)] Venn diagrams. -t-[X*T*Z*/(0,0,l)l+[X*1'*Z*/(0,0,0)] Figures 2.2-2a-d represent Equations 2.2-6 a-d, ./(UI)=(l*l)+(0*l) = I (2.2-8a) (2 2 8b) or2.2-8a-d. These are barriers bounded by lines but m'o^âtoHot?)"!) '" not intersected by any lines. Thus, they are elemental /(lAO)=(l *0)+(0 * 1)=0 (2.2-8c) units called "minimal cutsets." The termX*F is JKCu',l)=(0*lMl*0 = l (2-2~M} represented by Figure 2.2-2e. Notice the area is cut by A, this becomes equation 2.5(2.5-41) 43, where A is the failure rate and u is the ^' "' repair rate. Equation 2.5-43 is a definition of _ M + A * e xp[-(A+u)*?] (2.5-42) "availability." Since 1/u = MTTR (mean time to A +u repair) and i/A = MTTF (mean time to failure) A more f)( ^ conventional definition is given by 2.5-44. (2.5-43) A +(i Unavailability = / availability. If u >A, it is, MTTF asymptotically, found from equation 2.5-43 to be Availability MTTF + MTTR (2.5-44) equation 2.5-45, where T = 1/u is the mean time between repairs. While not shown here, if a system has k redundancies of identical subsystems, each with failure (2.5-45) rate A and repair period r, the equilibrium unavailability is (2.5-46) given by equation 2.5-46. Table 2.5-2 Mean Variance and Moment-Generating Functions for Several Distributions* E(x) var(x) f(x) Mx{6) Distribution Binomial

in} n \*pm*(\-prm \m)

n*p

Poisson Exponential Rayleigh Weibull

;xp{-n)*nx/x! X,*exp(-A*x) K*x*exp(-K*x2/2) K*xra* EXp(-K*x m+ V(m+l) x°*exp(-x/p)/

u 1A

Gamma

+!

;p« *r(«+i)]

Ait/(2*K) [K/(m-fl)]-"m+1* r[(m+2y(m+J)] 3*(o+l)

n*p*(l-p)

[l+p*(exp(8)-l)r

u

exp(A)*fexp(0)-l] •A/{9-A) complex complex

I/A2 3.429/K {[K/(m+l)]'-a*r(6)tE(x)]2};6=m+3/m+l 32*(a+l) 2

.(i/pr1a+i/ (0-i/p)

a exp(n*6+02*o2/2) exp[-(x-M)2/2*02]/ u fo*/(2*n) * Reprinted from M. Schuman Probabilistic Reliability: An Engineering Approach. 2nd Edition, Copyright, Robert E. Krieger Pub. Co., 1988, Sformal

2.5.5 Summary of Functions and their Generating Functions Table 2.5-2 provides a convenient summary of distributions, means and variances used in reliability analysis. This table also introduces a new property called the generating function (MX0). 49


Generating functions are used in calculating moments of distributions for power series expansions. In general, the nth moment of a distribution,/(#) is: E(x ") = Jjc" *f(x) *dx, where the integration is over the domain of x. (If the distribution is discrete, integration is replaced by summation.) A generating function is defined by equation 2.5-47. To illustrate it use, Table 2.5-2 gives the generating function for an exponential distribution as: -A,/(6-X). Each moment is obtained by successive differentiations. Equation 2.5-48 shows how to obtain the first moment. By taking the limit of higher derivatives higher moments are found.

2.6 Bayesian Methods The Reverend Thomas Bayes, in a posthumously published paper (1763), provided a systematic framework for the introduction of prior knowledge into probability estimates (Crellin, 1972). Indeed, Bayesian methods may be viewed as nothing more than convolving two distributions. If it were this simple, why the controversy? The controversy (for a lucid discussion refer to Mann, Shefer and Singpurwala, 1976) between "Bayesians" and "classicists" has nothing to do with precedence, for Bayes preceded much of classical statistics. The argument hinges on: a) what prior knowledge is acceptable, and b) the treatment of probabilities as random variables themselves. Classicists believe that probability has a precise value; uncertainty is in finding the value. Bayesians believe that probability is not precise but distributed over a range of values from heterogeneities in the database, past histories, construction tolerances, etc. This difference is subtle but changes the two approaches. Bayes's methods aim to M satisfy two needs: the concept of ^ = I exP(0 **) */W *^ (2.5-47) probability as degree of belief, ,. ~ ,and the need to use all available E(x) = Q^d[-X/(Q-A)]/36 = 0_0*/(6 ~A) 2 = I/A (2,5-48) information in a probability estimate. Classicists reject all except test information. However, a Bayesian believe that prior information from related work, laboratory tests, codes, quality control, etc. should be used to decide the state of belief in something's operability. The problem is in quantifying this prior knowledge. This section develops Bayes's equation and presents results for some distributions using conjugate functions. It closes with confidence interval estimating.

2.6.1 Bayes's Equation Equation 2.4-2 may be considered to be composed of three variables (Tribus, 1969) as shown in equation 2.6-1, where P(.A *B\E) is read as the probability of A and B given E where A, B, and E are observables. (E represents the operating environment.) 50

P(A*B\E)=P(A\B*E)*P(B\E) p^ ^B\E} = pm *A\E)

(2.6-1) (i 6-2)

Bayesian Methods

However, equation (26-3) P(A*nE)=P(B*A\E)=P(AV*E)*P(mE)=P(®A*E)*P(A) 2.6-2 is valid because A, B are commuting variables that lead to equation 2.6-3. Rearranging, results P(B\A (2,6-4) in one of the usual forms of the Bayes equation (equation 2.6-4). P(AIE) is the prior probability of A given E. P(B\A*E) is probability that is inferred from new data (call it "update"), and P(A\B*E) is the posterior probability that results from updating the prior with new information. The denominator P(B\E) serves the purpose of normalization. From the completeness of the Aj's (the components of A) and using the multiplication rule for intersection, equation 2.6-5 is obtained. Equation 2.6P(B\E) = SP(5*A.LE) (2.6-5) 6 results from the product rule. Bayes equation may < be written as the more useful equation P(BIE) = SPC*W.*E)*/>(A,lfi) (2.6-6) 2.6-7, for discrete A/, and as equation ' ; 2.6-8 for continuous A's over the domain P(A\B *£) - n *f(Aw,) _ of A. Equations 2.6-7 and 2.6-8 show ZP(B\Ai*E)*P(Ai\E) that the updated probability is just the ' P(B\A*E)*P(A\E) product of the rprior and the new P(A\B*E)= . — 77 (26-8) . , . IJ P(B\A.*E)*P(A\E)*dA l^-o o; inforniation. ^ ' ' ' Now that the point has been made that all variables are conditioned by the environment, E will be dropped from the notation because it is implied. Example of the Use of the Bayes Equation

Suppose two equal lots of bolts were supplied to an aircraft manufacturer. Fifty percent of the bolts in lot A, are excessively hard, and 10% in lot A2, but the identity of the lots was lost. The problem is to determine the probability of lot identification by sampling, using equation 2.6-7 and the prior knowledge related to the fractions of bad bolts in each lot. Let B be the failed test, then the probability of B, if it were from lot A, is P(BIA,) = 1 - 0.5 = 0.5, and if B is from lot A2, P(BIA2) = 1 - 0.9 = 0.1. The denominator is: P(BIA,) P(A,) + P(BiA2) P(A2) = P(B). Inserting values: 0.5 * 0.5 + 0.1 * 0.5 = 0.3. Hence, the probability that lot B was selected from A,, given the evidence of B. is: P(A,IB) = P(A1)*P(BIA,)/P(B) = 0.5 * 0.5/0.3 = 0.883. The probability that it was selected from A2 is: P(A2IB) = P(A2) * P(BIA2)/P(B) = 0.5 * 0.1/0.3 = 0.167. 2.6.2 Bayes Conjugates for Including New Information There are two special cases for which equations 2.6-7 and 2.6-8 are easily solved to fold a prior distribution with the update distribution to obtain a posterior distribution with the same form as the prior distribution. These distributions are the Bayes conjugates shown in Table 2.6-1.

51


This table indicates that if a beta function prior is Table 2.6-1 Bayes Conjugate convoluted with a binomially distributed update, the Self-Replication combination (the posterior) also is beta distributed. Prior Update Posterior Similarly, prior information distributed as a gamma beta -* binomial beta function with an exponentially distributed update gives a gamma -* exponential -* SEM5§___ posterior that also is gamma distributed. For both conjugate distributions, since the posterior is the same as the prior, this process may be repeated as many times as desired. A double application is called a "two-stage Bayesian update," Bayes conjugates provide a simple, easy way to implement Bayes' equation without using the summation or integration required by equations 2.6-7 or 2.6-8 for arbitrary distributions, 2.6.3 Constant Failure Rate Model If the failure distribution of a component is exponential, the conditional probability of (2.6-9) /?(MIA*0 = T(r-l) observing exactly M failures in test time t given a true (but unknown) failure rate A and a Poisson distribution, is equation 2.6-9. The (2.6-10) continuous form of Bayes's equation is equation 2.6-10. The Bayes conjugate is the gamma prior distribution (equation 2.6(2.6-11) r(4>) 11). When equations 2.6-9 and 2.6-11 are substituted into (2.6-12) /?(AW*f)=equation 2.6-10 and the integration is performed, the posterior is given by equation Table 2.6-2 Effect of Bayes Conjugation on a Gamma prior 2.6-12 which is also gamma distributed as it should be. Prior Update Posterior Table 2.6-2 (upper) shows that a gamma prior t t+T (equation 2.6-11) updated with exponential data produces M CJH-M a gamma posterior (equation 2.6-12) by adding T to t and M Prior Posterior Statistics * to (p. Because the prior is derived from other than test data, (<jM-M)/(m) E(A) (fr/T Tis called pseudo-time and pseudo-failure. The mean, 0 /(<JH-M)/(T-H)2 /(<j>/T ) E(A) and standard deviation, a, of the prior and posterior are given by Table 2.6-2 (lower). 2

2.6.3.1 Confidence Estimation for the Constant Failure Rate Model To obtain the confidence bounds, the posterior distribution (equation 2.6-12) is integrated from zero to A,', where A' is the upper

52

(

dk

• * e x '-y)*ya-1 T(a)

(2.6-13) (2.6-14)

(2.6-15)

Bayesian Methods

bound on the failure rate with fractional confidence a. The result is the incomplete gamma function (equation 2.6-14 from Abramowitz and Stegun (1964) - equation 6.5.2). Let y = (t+ r)*/£, dy -(t+ T)*dA, a = 0+M, and x and equation 2.6-15 is obtained. (2.6-16) Using equation 26,4.19 from Abramowitz and Stegun, 1964 and changing to conventional notation, results in equation 2.6-16. This says that the failure rate is less than or equal to the inverse cumulative chi-squared distribution with confidence a and degrees of freedom equal to twice the number of failures including pseudo- failures divided by twice the time including psuedo-time. 2.6.3,2 Truncated Gamma and Step Prior

It may be decided that the gamma prior cannot be greater than a certain value x?'. This has the effect of truncating the normalizing denominator in equation 2 .6-10,m 2 and leads to equation 2.6-17, where P(Xo/v) is the cumulative ., *«*f(x^v).2*(M*4>) ^6-17) integral from 0 to tf over the chi-squared density function ~ 2 *(t+T) with v degrees of freedom, a is the prescribed confidence p^\ - j ^ Â,° truncated gamma prior is to modify the confidence interval to become an effective confidence interval of a *jP(%2 * v(y) +2 * v(x) (2.7-11) If two distributions :c and y are combined additively (equation 2.7-6) the mean and variance are given by equations 2.7-7 and 2.7-8. If two distributions are combined multiplicatively (equation 2.7-9) the mean and variance are given by equations 2.7-10 and 2.7-11. These results, presented without proof, are important and hold for any independent physical distributions. In words, they say that the mean of a sum is the sum of the means; the mean of a product is the product of the means for any distribution. Furthermore, the variance of the sum is the sum of the variances, and the variance of the product is the product of the variance plus the mean of one variable squared, times the other variables' variance, plus the converse - again for any distribution. When the point values are average probabilities, the overall result from combining systems as combinations of sequences and redundancies is found by simply combining the mean probabilities according to the arithmetic operations. 2.7,3 Taylor's Series Suppose a system is a function of its components (equation 2.7-12). Expand the function / about the mean values of its arguments in a multivariable Taylor series (equation 2.7 -13). The mean of Q, which is the expectation of equation 2.7-13, is equation 2.714, where the variance of Xj and the covariance of ^ and Xj are given by equations 2.7-15 and 2.7-16 respectively.

Q=f(Xl,XT-~Xn)

(2.7-12) (2.7-13)

• 1/2 * S (drffdXf)

*(X,. -<X.:

i=l

n-l n

+2*2 E

(&fldXldX)*(Xi-<Xt>)*(Xi-<Xj>)

'

Q =/«*,>, <X2>, - - -<X>) +1/2 * S (82f/dXf)

*n2(X.)

n-l n

+ S E (SPffdXJdX) i=\j=i+l

51

*E(X-<X>) *(Xj-<X >)+,..

(2-7-14)


The covariance is zero . .. • U1 when the variables are uncorrelated. The variance of Q can be obtained from equation 2.7-17. £"( ' j j • u~(X)=E(X.-<X>) r2V v !

Case 1 Union For the special case that the system model is the o = f(X X } + S X sum of probabilities (equation 2.7-19) with equation '"" " / = [ ! 2.7-18 gives the result: equation 2.7-20. This says that « the system mean is the sum of the means of & ~ ^î the component distributions. « Equation 2.7-18 for the system U = variance is equation 2.7-21. Since the (S) 2u 2 2(J^.) ,,^ „ covariance of uncorrelated variables is zero, this becomes equation 2.7-23 (i.e., the +2 * S S E[(X.-<X.>)(X.-<X.>)] system variance is the sum of the /-i;=«+i component variances). u(O) = Su(X) Case 2 Intersection If the system distribution is the product of the component distributions (equation 2.7-23), the mean is given by equation 2.7-24 which, for uncorrelated variables becomes equation 2.725 ' Hence, the previous result that the system mean is the product of the component means is validated. Equation 2.7-18 gives i • j • the variance as does equation 2.7-26, which for uncorrelated variables becomes equation 2,7-27. If specialized to two

Q=f(Xl...Xf)

+ IlX.

i i _. :^ ,, = II<X> ' M «-i « ^ < > +2 s s * * *£Kx«"Kxr<X/>)] J j '* ' n = II<J.> 1=1 » ^n 2^ //*i\ \^ ii^ /"^ \ ^2^^ ~ •"—~—*M 2 (A / J + '"' ' n-\ n 2 +2*S S £T(X ~<X>}2*(X; -<X>) ] ; i=i;=/+i ' ' " "_! " ^2(6) = x^W* % S H2(X,)*|i2(X;)

58

._ . 2.7-15) ' p7n

n~

U- /-Is)

(27-19) (2.7-20) (2.7-21)

(2,7-22) (2.7-23) n i o/i \ (2./-24)

(2.7-25)

/O **7 Orf£"\

'^- '"-4'0/

(2.7-27)

Uncertainty Analysis

components, equation 2.7-27 is the same as the equation obtained by the moments method, 2.7.4 Monte Carlo This is a technique developed during World War n for simulating stochastic physical processes, specifically, neutron transport in atomic bomb design. Its name comes from its resemblance to gambling. Each of the random variables in a relationship is represented by a distribution (Section 2.5). A random number generator picks a number from the distribution with a probability proportional to the pdf. After physical weighting the random numbers for each of the stochastic variables, the relationship is calculated to find the value of the independent variable (top event if a fault tree) for this particular combination of dependent variables (e.g., components). 2,7.4.1 Direct Simulation In direct simulation, the distribution of A is simulated by selecting values distributed according to its pdf; then the experimental distribution of failure is simulated by having ones and zeros distributed according to the values of A. From a set of trials, various combinations of zeros and ones corresponding to the component's operability state are selected and input to logical equation to determine if failure occurred. By repeating this process many times, the failure probability distribution is found. Clearly this is a very slow process. Suppose the tree has two redundant components with mean failure probabilities of 1E-2, then the system failure probability is 1E-4 which occurs only once in ten thousand samples. In a counting problem the standard deviation is estimated as 1/-/N where N is the number of counts. If 10% accuracy is desired: 0.1 = 1/-/N and N-iOO. But failure only occurs once in ten-thousand trials hence one-million trials are needed for 10% accuracy. While this outlines the concept, such real 11 time simulation generally is not practical for lun 1 determining the reliability of safety systems. 210 However, a direct simulation of safety system ds reliability that was performed used the electronic "£ simulator, ERMA (Rothbart et al., 1981), in which £ 9 Steady State special purpose electronics accelerated time by 1E10, | so that a million years of plant life required about > one hour of simulator time. Figure 2.7-1 shows the results of a simulation of the reliability of a low 10 20 30 40 50 60 Elapsed Time in Thousands of Reactor Years pressure cooling injection system for a reactor that Fig, 2,7-1 ERMA simulation of a low pressure was simulated using ERMA. It exhibits a phenomenon called "voter statistics," that is, a candidate that coolant injection system. The absence of oscillations convergence is evidence of voter statistics. gets ahead, is likely to stay ahead rather than exhibit in theReprinted with permission ofEPRI, USA oscillations about the steady-state value. This figure provides a caution in interpreting PSA results, namely, that a very large amount of experience is 59


needed to reach the steady-state value—the asymptotic probability. Scatter by a factor of 2 is not surprising. These remarks are particularly appropriate in trying to draw statistical conclusions regarding the single event: TMI-2. 2.7.4.2 Simulation of Distributions" In the previous discussion, if all the failure rates are selected by random sampling from their distributions and these values are used directly in the exponential model with component replacement by their probability, the probability Failure probability, x of the top event may be calculated. By sufficiently sampling Fig. 2.7-2 Histogram of probability of the distribution of the As, the distribution of the top event distribution generated by Monte Carlo probability is determined. The result is a histogram with simulation. The height of each bar is the number of counts in the interval each bar uncertain by the counting statistics. Figure 2.7-2 illustrates such results. To determine the amount of sampling required, suppose it is desired that the 95% wings are to be determined to 10%. This implies about 100 counts in each of the wings. But, by definition, only 5% of the area are in these locations. By proportion 200/10% = N/100%, so about 2,000 samples would be needed, fewer if there is a priori information regarding the forni of the distribution; in which case the Monte Carlo process provides parameter fitting for the a priori distribution.

2.7.5 Discrete Probability Distribution (DPD) For each component in a system, there is a distribution like Figure 2.7-2. Each bar may represent an ordered pair (xjt Pj) where xl is the value of the variable and P; is the probability of the value xja.

2.7,5.1 Union (Addition) Consider the union of only two components (equation 2.7-28), where x} and x2 are each distributed as Figure 2.7-2. If there were only one bar in each histogram, the values x, and x2 would be added and the probabilities multiplied as the probability of joint occurrence (equation 2.7-29).

(2.7-28) (2.7-29)

" This method was used in the Reactor Safety Study. 0

In this discussion, Xj is the probability that a system's component will fail and Pj is the probability that it has the probability xr This confusion is avoided by just considering x} as a variable.

60

Sensitivity Analysis and Importance Measures

For each distribution with a number of bars, start with the first bar of the first distribution and add successively all combinations of the bars in the second distribution, then go to the r second bar of the first distribution ?=( }(x +rA21'Ml P *P x +x P *P . . ., and . add ,all *• ^n^21'Ml ^21^*U 2F} vn ^ -1-'401 ' ->UJ combinations of the second distribution, and so ^ +x p .^p \/x +x p *p \ on until all combinations have been executed. " H 21 To generalize, let xln represent the nth abscissa of the first distribution and PlH the (xln+x2l,Pn*P2l)(xu+x2l,Pn*P^) corresponding ordinate of a normalized distribution. Then z is formed of the ordered pairs (equation 2.7-30). As an example, for x, x, = (-l,0.1)(l,0.5)(2,0.4) (2.7-31) (equation 2.7-31), and x2 *2 = (5,Q.2)( 10,0.8) (2.7-32) (equation 2.7-32 - each is a bar z = (4,0.02)(6,0.1)(7,0.08)(9,0.08)(11,0.4)( 12,0.32) (2.7-33) in the histogram), we get equation 2.7-33. It should be noted that the resulting distribution is normalized. (This may be checked by adding all the second pair numbers.) 2.7.5.2 Intersection (Multiplication) Suppose the components are redundant, then their probabilities, if independent, are combined by multiplication (equation 2.7-34). this z = ( x *x ) is generalized by analogy with the preceding (equation 2.7-35). As a numerical example, if the distributions z=(*,, *x2l,P,, *P2l)(xl, *x2l,Pl, *P21) Xi and *2 in equations 2.7-30 and 2.7-31 (X[ j *jt21 ,P,, *P2n)(xl, *x2l,Pl {*P2,) are combined in multiplication, the results is equation 2.7-36. A bit of reflection shows that DPD is a (înî'^nîXûî'^n*^!) numerical implementation of convolution integration described in Section 2.7.1.

^ 7.34) (2.7-35)

2.8 Sensitivity Analysis and Importance Measures 2.8.1 Sensitivity Analysis When a risk or reliability analysis has been performed, it is appropriate to inquire into the sensitivity of the results to uncertainties in data. One type of sensitivity analysis is the effect on system reliability that results from a small change in a component's failure probability. A problem in doing this is determining the amount of data uncertainty that is reasonable. The amount of change 61


may be judgment or the parameter may be taken to the extreme of the data range even though such extremes may be rare. Significance of risk contribution may be done by ordering the risk contributors from most-to-least (rank order), but because of the arbitrariness of variation of the variables, this may be meaningless, A more systematic approach is to calculate the fractional change in risk or reliability for a fractional change in a variable. As an example, suppose risk is composed of failure probabilities p}, p2, ... p3 i.e. R = R(p ,, p2, ,.,p?). The total derivative is equation 2.8-1, where each of the partial derivatives are taken with the uninctuded vari,n ,-,„/-, x , / a n / n \ i /^«/-> \ j -nj? / ables held constant. The partial derivdR-(dR/dp (2,8-1) ])*dpl+(dR/dp,)*dp2+...^dR/dpf)*dpn=Xfi*dp! atives are multipliers f-t that multiply the change in p, The larger the multiplier, the more significant that component is to the overall risk. Thus, the/ '5 measure the sensitivity of the i-th component's probability of failure. A disadvantage of this sensitivity measure is in determining the size of the uncertainty in dp{, 2.S.2 importance Measures

A number of risk importance measures have been defined for the interpretation of PSAs and for use in prioritization of operational and safety improvements. Some of these measures are similar to sensitivity defined as the total derivative (equation 2.8-1). a) Birnbaum Importance - is the change in the risk for a change in the failure probability for a component or system (the same as/ in equation 2.8-1). Equation 2.8-2 is the Birnbaum importance for the i-th component, where R (risk) is the dependent variable, /?, (probability) is the failure probability of the i-th component. While Birnbaum Importance identifies systems important to safety, it does not consider the likelihood of component failure. ,B _ dR „ That is, highly important but highly reliable passive components ' have a high Birnbaum Importance. To overcome this problem, , -„._ ,_ ., _. TInspection *• Importance r t i *A *i=P; (2.8-3) was formulated. ' ' *aR/dp.• FV clRIR b) Inspection Importance - is Birnbaum Importance J = . (2.8-4) dp/Pi multiplied by the probability of failure of the component of concern equation 2.8-3). This is the same as unnormalized Fussell-Vesely Importance. c) Fjissgfll-Vesely. Importance11 - is the fractional change in risk for a fractional change in component failure probability (equation 2.8-4). A problem with Fussell-Vesely importance is in determining the risk used for normalization. Should it be total risk or partial risks? If the measure is only used for prioritization, it does not matter.

p

In Fussell-Vesely importance it is common to set the risk normalization to S. 62

Sensitivity Analysis and Importance Measures

Inspection Importance is Fussell-Vesely Importance with the risk set to I. Vesely introduced several other importance measures called "worths," d) Risk Achievement Worth Ratio fRAWR^ - is the ratio of the risk with the i-th component failed to the risk with no components assumed to be failed. This is shown in equation 2.85, where R* means the risk with i-th component failed.

JAR _ _"j_ ' R

^ >••"-

(2,8-6) (2.8-7)

li^R-R]

(2.8-8)

ni

f) Risk Reduction Worth Ratio f RRWR) - is the ratio of the nominal risk to the risk that results with the i-th component perfect. This is equation 2.8-7, where R ( means the risk with the i-th component having a failure probability equal to zero. g) RJSJC Reduction Worth Increment (RRWI) - is the incremental change in risk that results from the i-th component being perfect (equation 2.8-8). 2.8.3 Relationships between the Importance Measures Importance measures the contributions of various components to the probability of system failure in the form of a cutset equation (Section 2.2). A cutset equation has the form of a sum of products of probability. As such it is linear in the probabilities. The sequences involving the i-th component R = Sp. *A + B (2.8-9) may be separated from the other sequences and this , B , „. , , , . , . „ , ,. , ,. /,• =A. Birnbaum (28-10) probability factored from the sum of products as ' \ •• > shown in equation 2,8-9, where At is the cutset with /, =P, *A; Inspection (2.8-11) Pi factored out. This property relates the A. FV 7 importance measures. Substi/ =Pi*-jj Fussell-Vesely (2.8-12) luting equation 2.8-9 into ^ = V^ RiskAchievement WorthRatio (2,8-13) equation 2.8-2 gives equation 2.8-10. Similarly substituting R equation 2.8-2 into equation /f=A.+#-/e Risk Achievement Worth Increment (2-8-14) 2.8-3 gives equation 2.8-11. 'RR R Eliminating A between '/ = — Risk Reduction Worth Ratio (2.8-15) equations 2.8-10 and 2.8-11 ^» gives the equivalence I^-R-B Risk Achievement Worth Increment (2.8-16) between Birnbaum and Inspection importances 63


(Table 2.8-1, 2). Following the same procedure produces an equivalence between Birnbaum and Fussell-Vesely importances (Table 2,8-1,3). Achievement Worth Importance requires failing the i-th component by setting its probability to one: p f ~ 1 as shown in equations 2.7-13 and 2.7-14. Substituting for Af from 2.8-10 gives the equivalences in Table 2.8-1, 4 and 5). The Reduction Worth Importances require that the system or component be made perfect by setting the probability to zero: p( 0 (equations 2.8-15 and equation 16). A, and B may be eliminated to relate one importance to others (Table definitions,

Table 2.8-1 Relationships between Importance Measures

# Measure

Definition

Equivalence

I

I* = dR/dp.

-

Bimbaum

2 Inspection

I i=pi*dR/dpi

=p.*i,J9 i

3 Fussell-Vesely

I™=dR/R/dp/p.

= Il/R

l

4 Risk Achievement Worth I™ = R]/R

••=l+(/f-/^//?

5 Risk Achievement Worth /f =R]-R

--/,.-/,. /* il

Ratio

Increment

6 Risk Reduction Worth Ratio

7 Risk Reduction Worth Increment

I**=R/R~i

=*/(/?-/',)

/f =/?-/?:

^/T

"

2.8-1,6 and 7). This table also summarizes the importance

2.8.4 Interpretation and Usage

The relationships between the importance measures is based on the assumption that the systems are not reconfigured in response to a component outage. If this is done, the basic definition of the importance measure is still valid but there is not such a simple relationship. Disregarding mis complication, some interpretations of the importances may be made. The Birnbaum Importance is the risk that results when the i-th system has failed (i.e., it is the A{ term in Equation 2.8-9). Inspection Importance and RRWI are the risk due to accident sequences containing the i-th system. Fussell- Vesely Importance is similar except it is divided by the risk so may be interpreted as the fraction of the total risk that is in the sequences contains the Q-th system. The Risk Achievement Worth Ratio (RAWR) is the ratio of the risk with system 1 failed to the total risk and is necessarily greater than one. The Risk Achievement Worth Increment (RAW!) is the incremental risk increase if system 1 fails and the Risk Reduction Worth Ratio (RRWR) is the fraction by which the risk is reduced if system 1 were infallible. Figures 2.8-1 and 2.8-2 from Vesely et al. (1983) show how the RAWR and RRWR measures vary for two PWR nuclear power plants (Oconee, and Sequoyah) based on their PSAs. This variation may be explained on the basis of different manufacturers of the plants (Babcock & Wilcox and Westinghouse, respectively) It has been suggested that the rank ordering of systems is about the same regardless of the importance measure that is used. Table 2.8-2 is the result of a cluster analysis (judgement of trends) in Indian Point-3 system importances with clustering into 5 groups designated A through E, This

64

Summary

1E4\

c

c iS

t

,

w £

CL

ic

1 I100 10

1

*

(X. '

i

I I

J1! 5: o a - v, ^ S ® a c -c

*~

U4 , |>

1

head s&rv. water \ action \

'~

\Lowpres. inj. }' | Pms. relief valve

S LU

I I Emer. cool, recin

~

1E3

6

1 Relief valve

Reactor protect sys.

Auxiliary feedwater

RRWR

o o

-JL

•^ o

oc ^ o:

,,__._ 1 1-

c

ts CO c

Q. *

I

o o o c contact properties, process technology, and process equipment is essential to the PSM program and to a process Steam Waste Water hazards analysis (PrHA). This Stripping information serves many users including the PrHA team. The needed chemical information includes: fire and explosion characteristics, reactivity hazards, safety and health hazards and the corrosion and erosion effects. Current material safety data sheet (MSDS b ) information helps meet this requirement, but must be supplemented with process chemistry information regarding runaway reactions, and over-pressure hazards. Process technology information includes diagrams such as Figure 3.1.3-1, and criteria for maximum inventory levels for process chemical limits beyond which the process is considered to be upset. Also included is a qualitative estimate of the consequences that Fig. 3 1.3-1 Example of a Block Flow Diagram could result from deviating from the limits. A block flow diagram is simplified to show the major process equipment, interconnecting process flow lines, flow rates, stream composition, temperatures, and pressures. Process flow diagrams (Figure 3.1.3-2) are more complex. They show all main flow streams, valves, vessels, condensers, heat exchangers, instrument locations, reflux columns, etc. Pressures

b

MSDS are available from the Chemical Abstract Service of the American Chemical Society (ACS), 1155 16th St. NW Washington DC 20036, or the Internet at http//www.acs.org, and from the chemical manufacturer. A general website to these is: http://hazard.com/ 68

Guidance from the PSM Rule

and temperatures on all feed and product lines to enhance the understanding of the process. They show materials of construction, pump capacities, compressor horsepower, and vessel design pressures and temperatures. In addition, major components of control loops are usually shown along with key utilities, Piping and Instrument diagrams (P&IDs - not shown) may be even more appropriate for showing these details and to provide information for PSA. The P&IDs are used to describe the relationships between equipment and instrumentation and other relevant information that enhances clarity. Fig. 3.1.3-2 Process Flow Diagram Computer software programs, fault trees and event trees are other diagrams that provide useful information. This information documents the process equipment design and provides a "paper trail" to the codes and standards used in the engineering. Such codes and standards are published by such organizations as the American Society of Mechanical Engineers, American Petroleum Institute, American National Standards Institute, National Fire Protection Association, American Society for Testing and Materials, National Board of Boiler and Pressure Vessel Inspectors, National Association of Corrosion Engineers, American Society of Exchange Manufacturers Association, and model building code groups. In addition, various engineering societies issue technical reports which impact process design. For example, the American Institute of Chemical Engineers (AIChE) publishes technical reports on topics such as two phase flow for venting devices. Referencing and using such technical reports is good engineering practice. Existing equipment that may have been designed and constructed many years ago according to codes and standards no longer in use, requires identifying the codes and standards that were used, and the aspects of the facility and process affected. To justify that it is still suitable for the intended use may require testing, inspection, and demonstration. If the process involves departure from applicable codes and standards, the suitability of the design and construction must be documents.

69

Chemical and Nuclear Accident Analysis Methods

3.2 Process Hazard Analysis 3.2.1 Overview Process hazard analysis d(PrHA) is one of the most important elements of a process safety management program. A PrHA is an organized and systematic effort to identify and analyze the significance of potential hazards associated with the processing or handling of hazardous chemicals. PrHA information assists management and employees decide on safety improvements and accident consequence reductions. A PrHA is directed toward analyzing the risk of fires, explosions, releases of toxic or flammable materials. Equipment, instrumentation, utilities, human actions, and external factors are considered in the process. Selection of a PrHA methodology requires consideration of many factors including the availability of process information such as: experience with the process, changes that have taken place, reliability, aging, maintenance, etc. If it is a new process, less reliance can be placed on experience and greater reliance must be placed on the analysis of possible accidents and accidents in similar or related processes. Size, complexity and hazard severity influences the choice of the most appropriate PrHA methodology. Simplifying assumptions used by the PrHA team and reviewers must be understood and recorded to indicate the completeness of the PrHA, and for use in future improvements of the analysis. The PrHA team and especially the team leader must thoroughly understand the methodology that is selected A team consists of two or more people that know the process technology, design, operating procedures, practices, alarms, emergency procedures, test and maintenance procedures, routine and non-routine tasks. They must consider: authorization and procurement of parts and supplies, safety and health standards, codes, specifications and regulations. The team leader provides management and goals to the process; the team and consultants construct and interpret the analysis. PrHA may use different methodologies for different processes depending on the size, complexity and age of the facility by using team members that are expert for analyzing their assigned process. For example, a checklist may be used to analyze a boiler or heat exchanger, with a HAZOP for the overall process. Batch processes of similar subsystems may be analyzed with a generic PrHA that is modified according to differences in components, monomers or ingredient ratios. Small operations, although covered by the PSM rule, may use simplified methodologies and still meet the criteria. Businesses with similar processes and equipment may pool resources and prepare a generic checklist analysis used by all members to meet the PSM rule. If a PrHA is needed for many operations, the facility operator may prioritize the order of mitigating accidents. A preliminary hazard analysis (EPA, FEMA, and DOT, 1987) provides an overall risk perspective that can rankorders potential accidents by decreasing the number of affected individuals. Ordering may be based on maximum amounts and toxicity of the hypothetical releases, operating history of releases, age of the process and other factors that may modify the ranking. A PrHA assists in identifying improvements that give the most safety for the least cost.

70

Process Hazard Analysis

3.2.2 Operating Procedures and Practices Operating procedures specify the way tasks are to be performed, data to be recorded, operating conditions to be maintained, samples to be collected, and actions to enhance safety and health. Their accuracy, currency and utility is verified by the engineering staff and operating personnel. They include applicable safety precautions and warnings regarding: pressure limits, temperature ranges, flow rates, and the meaning and response to alarms and instruments. Procedures for startup and shutdown are included with the appropriate ranges for the process parameters. They include instructions and commands for computer process control, if used. Training uses operating procedures and instructions to define standard operating practices (SOPs) for use by control room and operating staff. Operating procedures must be current, and validated before use in refresher training. Management of change must be coordinated and integrated into SOPs, operating personnel oriented to the change, the change is then made and the process resumed. Upset and emergency training instructs the staff in their conduct under these conditions. It includes communications, mitigative actions, hazards of the tasks being performed, task closure, and reporting. 3.2.3. Employee Training All employees, working with highly hazardous chemicals must understand the safety and health hazards (29CFR1910.1200 - the Hazard Communication Standard) by knowing the properties of the chemicals with which they work, safe operating procedures, work practices, and emergency action. Training programs identify subjects, goals, and individuals to be trained. The learning objectives define measurable goals for the training modules. Hands-on-training using a simulator is important for control room operators. Technicians for test and maintenance and chemical processes benefit from hands-on training when reinforced with theory. Training using videos or OJT is effective. The training program prepares these personnel without the risk of learning with the hazards. Periodic evaluation of training programs is need to determine if the necessary skills, knowledge, and routines are being learned. Training evaluation is incorporated in the course design. If the employees, after training, have not learned what was expected, they must be retrained using changes that highlight their deficiencies. 3.2.4 Contractors Chemical process contractors to do hazardous work must provide personnel trained in performing the tasks without compromising health and safety. References, safety records, experience, job skills, work methods, knowledge and certifications provide evidence of competency. These records provide audit trails to assure management's safety compliance and to aid in incident investigations. 71


Contract employee safety is controlled through work authorizations that applies to all workers. Work authorizations allow management to safely coordinate contract employee activities with employee activities. 3.2.5 Pre-Startup Safety PrHA improves the safety, reliability and quality of the design and construction of a new or old process. P&IDs must be correct as constructed; operating, startup and shutdown procedures must be validated, and the operating staff must be trained before startup. Incident investigation recommendations, compliance audits or PrHA recommendations need resolution before startup. 3.2.6 Mechanical integrity The first line of defense is operating and maintaining the process as designed, to keep the hazardous material contained. The second line is the controlled release of materials through venting to containment/ confinement or through filters, scrubbers, flares, or overflow tanks. The third line includes: fixed fire protection systems (sprinklers, water sprays, or deluge systems, monitor guns, etc.), dikes, designed drainage systems, and other systems that control or mitigate hazardous releases. Equipment used to process, store, or handle highly hazardous chemicals must be designed constructed, installed and maintained to minimize the risk of release. A systematic, scheduled, test and maintenance program is preferred over "breakdown" maintenance" that could compromise safety. Elements of a mechanical integrity program include: 1) identification and categorization of equipment and instrumentation, 2) documentation of manufacturer data on mean time to failure, 3) test and inspection frequencies, 4) maintenance procedures, 5) training of maintenance personnel, 6) test criteria, and 7) documentation of test and inspection results. The first step of a mechanical integrity is the compilation and categorization of the process equipment and instrumentation. This includes pumps, pressure vessels, storage tanks, process piping, relief and vent systems, fire protection system components, emergency shutdown systems, alarms and interlocks. Mean time to failure data, and engineering judgment set the inspection and testing frequencies. Consideration is given to codes and standards such as: the National Board Inspection Code, American Society for Testing and Materials, American Petroleum Institute, National Fire Protection Association, American National Standards Institute, American Society of Mechanical Engineers and other groups.

c

Breakdown maintenance means no preventive maintenance (i.e., failure is annunciated by the fact of failure). 72


External inspection criteria are provided by these standards for: foundation and supports, anchor bolts, concrete or steel supports, guy wires, nozzles, sprinklers pipe hangers, grounding connections, protective coatings, insulation, and external metal surfaces. Internal inspection criteria are provided by these standards for: vessel shell, bottom and head, metallic linings, norimetallic linings, thickness measurements, erosion, corrosion, cracking, bulges, internal equipment, baffles, sensors and erosion screens. If a corrosion rate is not known, a conservative estimate, based on corrosion rates from the codes, is used. While some of these inspections may be performed by government inspectors, management needs an inspection program to ensure the tests and inspections are conducted properly and consistently. Appropriate training for maintenance personnel ensures they understand the preventive maintenance program. A quality assurance program ensures that construction, installation, fabrication, and inspection procedures are proper. The quality assurance program helps the first and second lines of defense. Quality assurance documentation includes: "As built", drawings, vessel certifications, verification of equipment, and materials of construction. Audits of the equipment supplier's facilities may be necessary to assure the quality of parts. Any changes in equipment must go through the management of change procedures.

3.2.7 Nonroutine Work Authorization The hazards of management-controlled nonroutine work in the process areas must be communicated to affected individuals. The work permit prescribes the procedures that must be followed to get the permit. Work authorization procedures specify: lockout/tagout, line breaking, confined space entry, and hot work authorization through clear steps leading to job completion. closure, and return to normal.

3.2.8 Managing Change Change in the PSM rule includes all modifications to equipment, procedures, raw materials, and processing conditions other than "replacement in kind." These changes are managed by identification and review prior to implementation. For example, any operation outside of the operating procedures' parameters requires review and approval by a written management of change. Changes requiring management are: process technology raw materials, equipment unavailability, new equipment, new product development, catalyst and operating conditions. Equipment changes include: materials, specifications, piping, equipment, computer programs and alarms and interlocks. Temporary changes have had dire consequences. Management must control temporary as well as permanent changes. Temporary changes must be time-limited to prevent their becoming permanent. Temporary changes are subject to the management of change that require provisions for the return to the original conditions. Documentation and review of these changes assures that safety and health considerations are incorporated in the procedures and process. A clearance sheet tracks the changes through the management of change procedures. A typical change form may include the description and purpose of the change, the technical basis for 73


the change, safety and health considerations, changes in the operating procedures, maintenance procedures, inspection and testing, P&IDs, electrical classification, training and communications, prestartup inspection, duration if a temporary change, approvals and authorization. Where the impact of the change is minor a checklist reviewed by an authorized person consulting with affected people may be sufficient. However, a complex or significant change requires a hazard evaluation procedure with approvals by operations, maintenance, and safety departments. Changes in documents such as P&IDs, raw materials, operating procedures, mechanical integrity programs, electrical classifications, etc., need noting so these revisions can be made permanent when the drawings and procedure manuals are updated. Copies of process changes are made accessible for operating personnel and the PrHA team. 3.2.9 investigation of Incidents Incident investigation is the process of identifying the underlying causes and implementing steps to prevent similar events from occurring. The incidents for which OSHA expects management awareness and investigation, are events that could have (near miss) or did result in a catastrophic release. Employers need in-house capabilities to investigate incidents that occur in their facilities. This requires a multidisciplinary team trained in the techniques of accident investigation capable of: conducting interviews, data gathering, accident modeling, consequence estimation, documentation and report writing. Team members are selected for their training, knowledge and ability. Personnel, where the incident occurred, are interviewed for preparation of a report of the findings and recommendations for dissemination as appropriate. 3.2.10 Emergency Preparedness Each employer must have an emergency preparedness plan in case of an unplanned release of hazardous material. This third line of defense mitigates an accident. Employees can mitigate small or minor releases, but major releases require additional resources in the form of local emergency response organizations. The emergency preparedness plans identify different levels of severity in the preparation of plans, procedures, training employees and implementing the plan. The emergency action plan facilitates prompt evacuation of employees. Upon an alarm; personnel evacuate to safe areas, cross or up wind if possible, assisting physically impaired people as necessary. Process buildings are not suitable refuges. Appointed, trained employees direct the emergency response to a minor release. 29CFR1910.120, the Hazardous Waste Operations and Emergency Response (HAZWOPER) standard covers plant personnel for a fire brigade, spill control, hazardous materials or first aid team. It addresses cooperative agreements between employers and state or local government emergency response organizations. Safety and health are the responsibility of employers and the on-scene incident commander and staff who are equipped and trained for emergency response. Drills, training exercises, and simulations, including the local emergency response team, are preparations for emergencies 74


Medium to large facilities enhance coordination and communication during emergencies with an emergency control center (ECC) that is composed of plant and local organizations and sited in a safe area for continuous occupancy throughout the emergency. It links the commander, plant management, and the local officials. The ECC contains a telephone, radio network, a backup communication network in case of power failure, the plant layout, community maps, utility drawings (fire water, emergency lighting), and reference materials (government agency notification list, company personnel phone list). It includes SARA Title III reports and material safety data sheets, emergency plans and procedures manual, a listing with the location of emergency response equipment, mutual aid information, and access to meteorological or weather data and any dispersion models.

3.2.11 Compliance Audits A trained audit team, consisting of one or more persons audits the process safety management system. The essential elements of an audit are: planning, staffing, conducting the audit, evaluation, corrective action, follow-up, and documentation. Advanced planning regarding the format, staffing, scheduling and verification methods are essential to the success of the auditing process. It provides a checklist that details the requirements of each section of the PSM Rule, lists the audit team members, serves as the audit verification sheet to expedite and to avoid omitting any requirements, and identifies elements needing evaluation or response to correct deficiencies. This sheet is used to develop follow-up and documentation requirements. The audit team members are selected for their experience, knowledge, training, familiarity with the processes and auditing techniques, practices, and procedures. The size of the team depends on with the size and complexity of the process. A large, complex, highly instrumented plant, may have members with expertise in: process engineering design, process chemistry instrumentation, computer controls, electrical hazards and classifications, safety and health disciplines, maintenance, emergency preparedness, warehousing, shipping, and process safety auditing. The audit includes a review of the process safety information, inspection of the physical facilities, and interviews with all levels of plant personnel. Using the procedures and checklist, the team systematically analyzes compliance with the PSM Rule and any other relevant corporate policies. The training program is reviewed for adequacy of content, frequency and effectiveness of training. Interviews determine employee knowledge and awareness of the safety procedures, duties, rules, and emergency response assignments. The team identifies deficiencies in the application of safety and health policies, procedures, and work authorization practices to determine corrective actions. Corrective actions are audit objectives. They address identified deficiencies, in addition to planning, follow up, and documentation. Corrective action begins with management review of the audit findings to determine appropriate actions and to establish priorities, timetables, resource allocations, requirements and responsibilities. Some corrective actions may be a simple change in procedure - subject to management of change. Complex changes require time for engineering studies and reviews. Taking no action is valid audit action; all actions require documentation.

75


UpUf HF

Fig. 3.3.1-1 Hydrogen Fluoride Supply System for providing HF6 to a fluid bed reactor to produce uranium letrafluoride for diffusive separation ofU-235from U-238. Gaseous HF is created by vaporizing anhydrous liquid HF in 850 Ib amounts in shipping pressure vessels. Nitrogen at 30 psig is applied to the top of the HF cylinder that is being weighed. HF is discharged to the vaporizer which is heated to vaporization at 25 psig by a hot water blanket. Safety components are the nitrogen pressure regulator and overpressure relief valves. Overpressure protection for the vaporizer is provided by relief valves connected to the top of the vaporizer and supply cylinder. 4 rupture disk protects the relief valves from exposure to corrosive HF. A tee between them to a manual vent and block valve that can be opened to relieve pressure for maintenance. Vent gas is released through a plastic hose to bubble through water in a plastic bottle to absorb offgas

Each deficiency, corrective action, schedule and responsibility must be recorded and tracked with periodic status reports, engineering studies, implementation and closure report. These reports are sent to affected management and staff.

3,3 Qualitative Methods of Accident Analysis This section describes how both hypothetical and real accidents are analyzed. These methods varying greatly in complexity and resource requirements, and multiple methods may be used in an analysis. A simple method is used for screening and prioritization followed by a more complex method for significant accident scenarios. Some methods give qualitative results; more complex methods give quantitative results in the form of estimated frequencies of accident scenarios. The process systems in Figures 3.3.1-1 and 3.3.1-2 are used in the examples.

76

Qualitative Methods of Accident Analysis

3.3.1 Checklist Pressure Check Valve A checklist analysis (CCPS, 1992) verifies Pressure Reducing Valve the status of a system. It is versatile, easy and applicable at any life-cycle stage of a process. It is Pressure primarily used to show compliance with standards Gage and practices by cost-effectively identifying hazards, chlorine Tank Checklists provide commonality for management Tower Water Basin review of hazard assessments. It may be used for controlling a process from development to decom- Fig. 3.3.1-2 Cooling Tower Water Chlorination missioning. Approvals by appropriate authorities Basin water is circulated by the pump through the venturi at 30 gpm. Chlorine gas, provided by a I ton verify each stage of a project. tank, is reduced to zero pressure by the pressure

reducing valve to he brought into the sitbatmospheric venturi. The pressure check valve

Description

A written list of items or procedures describe prevents chlorine gas flow unless the pressure m the the status of a system. Checklists may vary venturi is sub-atmospheric. If the first check w/w falh Morim wnitd considerably in level of detail, depending on the ' " process. The list identifies hazards, design deficiencies, and accident scenarios associated with process equipment and operations regarding: materials, equipment, or procedures. Checklists may be used for evaluating existing processes or contemplated processes. Developing a Checklist

A checklist analysis begins with a qualified team examining: the process description, P&IDs design procedures, and operating practices. As the checklist is developed, aspects of process design or operation that do not comply with standard industrial practices may be discovered by using detailed, process-specific checklists which be augmented by generic checkists for thoroughness. The completeness of hazard identification would be limited to the preparer's knowledge if not for the use of multiple reviewers with diverse backgrounds. Frequently, checklists are created Table 3.3.1-1 Possible Checklist Main Headings simply by organizing information from current Basic Process Considerations relevant codes, standards, and regulations. This Overall Considerations Operating Limits is insufficient, the checklist must be designed for Modes of plant startup, shutdown. the specific process including its accident construction, inspection and maintenance, experience. It should be a living document that is trigger events, and deviations of systems Hazardous conditions reviewed and revised from operating experience. Ways of changing hazardous events or Table 3.3.1-i (DOE, 1996) suggests main frequency of occurrence headings for a checklist. These are global Corrective and contingency action Controls, safeguards, and analysis heading starting with the process description, Documentation and responsibilities

77


overall considerations, operating limits, hazards and mitigation. Table 3.3.1-2 (DOE, 1996) is an example of the use of first and second headings. The first level are the global considerations (although not as global as Table 3.3.1-1) with the second level going to the more particular subject headings. This table begins with the site and its selection and goes to the process and hazards. Then it examines the process equipment, mitigation by storage selection, protection zones, fire protection and emergency planning. More inclusive is Table 3.3.1-3 which is appropriate at depth into the analysis. The major headings in this table address major hazardous subject areas, accident mitigation, protection and repair. For example, under the first major heading, "Storage of Raw Materials, Products, Intermediates," listed are: confinement measures, release mechanisms (valves), procedures for safe operation and limitations that must be observed for safety.

Table 3,3.1-2 Possible Headings and Subheadings Civil Engineering 1. Site Layout 1.1 Site Selection 7.1 Footings 1.2 Site Layout 7.2 Foundations 2. Process Materials 7.3 Drainage Systems 2.1 Physical Properties 7.4 Roads 2.2 Chemical Properties 7.5 Buildings 2.3 Toxic Properties 7.6 Additional Items 3. Reactions, Process Conditions, 8. Site Zones for Fire and Hazard Protection and Disturbances 8.1 Safety Considerations 3.1 Reactions 8.2 Zones 3.2 Process Conditions 9. Fire Protection 3.3 Disturbance Analysis 9.1 Introduction 3.4 Causes of Upsets 9.2 Buildings and Plant. 3.5 Abnormal Conditions 3.6 Critical Situations 9.3 Fire-Fighting 4. Equipment Organization 4.1 Introduction 9.4 Detection and Alarm 9.5 Classification of Fires 4.2 Design 4.3 Choice of Material 10. General Emergency Planning 4.4 Construction 10.1 Introduction 4.5 Location of Equipment 10.2 Operational 5. Storage and Handling of Dangerous Substances Emergency Situations 10.3 Release of Liquids 5.1 Storage 5.2 Handling and Gases 10.4 Fire and Explosion 6. Removal of Hazardous Wastes 6.1 Introduction 10.5 Personnel Protection 10.6 Training 6.2 Aspects of Disposal 6.3 Reduction of Disposal 10.7 Communications 10.8 Briefing and Information

Performing the Analysis

After preparation, a checklist may be used by less expert engineers than the preparers for inspecting the process areas to compare the process equipment and operations with the checklist either on hardcopy or laptop computer. The analyst fills in the checklist according to observations from their inspection, process documentation, and interviews with operators and their perceptions. Documenting Results

Qualitative results of checklist analyses vary, but generally the analysis produces the answers: "yes," "no," "not applicable," or "needs more information." The checklist is included in the PrHA report to summarize the noted deficiencies. Understanding these deficiencies leads to safety improvement alternatives for consideration, and to identified hazards with suggested actions. Figures 3.3.1-4 and 3.3.1-5 present checklist analyses of the Dock 8 HF Supply and the Cooling tower chlorination respectively.

78


Table 3.3.1-3 Simplified Process Hazards Analysis Checklist Storage of Raw Materials, Products, Intermediates storage Tanks Design Separations, Inerting, Materials of Construction Capacity, Drainage Dikes Demote Control - Hazardous Emergency Vaives Materials -lash Arresters, Relief Devices nspeciions. Procedures Temperature, Time Quantity .imitations Materials Handling belief Reverse Rotation, dentification, Materials of Construction, Leaks, Cavitation Explosion Relief, Fire Protection, Jucts Support Stop Devices, Coasting, Guards ronveyors, Mills Spills, Leaks, Decontamination procedures •Mpmg Ratings, Codes, Cross-Connections, vlatenals of Construction, Corrosion, Erosion Rates Process Equipment, Facilities and Procedures •Hirnps

^rocedures Content) ance

Personnel Protection Barricades, Personal Protection, Shower, Escape Aids Ventilation 3eneral, Local, Air Intakes, Flow Exposures Dther Processes, Public, Environment Jtilities solation: Air Water, hierts. Steam Toxicity. Flammabiiity, Reactivity. Hazards Manual Corrosion, Symptoms! First Aid Sampluig, Vapors, Dusts, Noise, Environment ladiation Controls and Emergency Devices 3

rotection

Controls

Ganges, Redundancy, Foil-Safe

Calibration, Inspection Marms nterlocks

•requency, Adequacy \dequacy, Limits, Fire, fumes Tests, Bypass Procedures

lelief Devices

\dequacy, Vent Size, Discharge, Dram, Support Dump, Drown, Inhibit, Dilute

Startup, Normal, Shutdown, Emergencies Emergency Fob Audits, Shortcuts, Suggestions 'rocess Isolation

identification

Zlectrieity, Heating, Coolant Air, nerts, Agitation Design, Materials, Codes, Access, vlaterials of Construction Vessels, Piping, Switches, Valves

Ditches

belief Devices

leactors, Exchangers, Glassware

Vents

leview of Incidents

3

Characteristics

inspections, Tests iazards Electrical

Vessels, Relief Devices, Corrosion iang-fires, Runaways \rea Classification, Gonformance, Purging Temperature, Pressure, Flows, Ratios, Concentrations, Densities, êvels, Time, Sequence 7'eroxides, Acetylides, Friction, ouling, Compressors, Static Electricity, Valves, Heaters •ieating Media, Lubricants, 'lushes, Packing Cooling, Contamination

..oss of Utilities Vessels

Operating Ranges gnition Sources Compatibility safety Margin

iant, Company, Industry

instruments

Sample Points 'rocedures

31ock Vaives, Fire-Safe, Valves 'urging, Excess Flow Valves \ir Quality, Time Lags, Reset Mndup, Materials ofConstruction Waste Disposal "lame Traps, Reactions, Exposures, Solids Discharge, Dispersion, Radiation, vlists 1 Sludge, Residues, Fouling. j viaterials i Sampling Facilities \ccessibility, Ventilation, V'alving ^lugging. Purging

Samples

Containeis, Storage, Disposal

Analysis

procedures. Records Feedback Maintenance

Decontamination Vessel Openings :> rocedures ;

ixed Protection

Extinguishers •ire Walls Drainage

79

Solutions, Equipment, Procedures Size, Obstructions, Access Vessel Entry, Welding, Lockout Fire Protection ~ire Areas, Water Demands, Distribution System, Sprinklers. Deluge, Monitors, Inspection, Testing, Procedures, Adequacy Type, Location, Training Adequacy, Condition. Doors, Ducts Slope, Drain; Rate

Chemical and Nuclear Accident Analysis Methods / able 3 31-4 Checklist Analysis of Dock 8 HF Supply Materials 1

Table 3.3.1-5 Checklist of Cooling Tower CMormation Materials

j ) include spare pigtails for the supply cylinders as ^f II as property rated ruptuie discs Other items must be ordered Protedurts }

\ es The> include spare pigtails for the supply cylinders as well as a lotameter and a pressuie check valve ' )tliei item

1' tltt; opt luting pttj*.tditreotential for excessive Daily testing of cooling open water chemistry corrosion in cooling water system otential personnel sressure sxposure and injury valves fail open and relief valve op_ens____ Failure Mode Too much flow through valve

Causes

Mitigation

Severity

Remarks

belief valve on pressure check valve outlet

[II

None

Automatic temperature controllers at most heat

tv

Skme

Pressure check fll valve located outdoors unlikely to accumulate significant concentration

Action item: Consider venting relief valve above around level

team reaches a consensus on each item's failure modes, causes, effects, detection methods, compensating provisions, severity, and remarks these are recorded. A more effective method than viewgraph projection, may be to use a table format in a computer with large screen display and record the consensus directly in the computer program. Staff requirements for a FMEA vary with the size and complexity of the process being analyzed. The time and cost of a FMEA is proportional to the size of the process and number of components analyzed. Two to four equipment items may be analyzed in an hour assuming all necessary information is available. If processes or systems are similar, the time for preparing an FMEA is reduced. Table 3.3.5-4 presents estimates of the time needed to perform a PrHA using an FMEA (CCPS, 1992). Limitations of Failure Mode and Effects Analysis

Human operator errors are not usually examined in a FMEA, but the effects of human error are indicated by the equipment failure mode. FMEAs rarely investigate damage or injury that could arise if the system or process operated successfully. Because FMEAs focus on single event failures, they are not efficient for identifying an exhaustive list of combinations of equipment failures that lead to accidents. 96


Table 3.3.5-3 Partial FMEAfor the Dock 8 HF Supply System Date: Plant: Item:

October 3, 1997 Y-12 Pressure reducing valve V- 13

Failure Effects Failure Causes Operating Mode Mode rfigh N2 pressure at Valve Internal Operation HF cylinders, HF open too ralve vaporizer vessel tar failure rupture - HF released o atmosphere Operator High HF flow to HF vaporizer - hijjh HF error low to B- 1 wing potential liquid HF to Calibra3-1 wing tion error Operation Internal ralve failure Operator srror Calibratio n error External Valve seal Operation leakage leakage

Valve closed too far

Page: 1/1 Preparers; RRF and JDC System: Dock 8 HF Supply System References: ORNL-XWQ 1 5396 Failure Detection Method Local pressure indication on Nj line

Local pressure indication between rupture disk and PRV-4 at vaporizer

Mitigation PRV-3 at V12 outlet

Severity

11

If N2 line relief valves lift, vaporizer relief valve should not lift. Relief valve discharges piped to D-wing stack

PRVs on N2 feed lines to HF cylinders PRV-4 at HF vaporizer None

EV

Mone Audible Waste on N2 f severe, same as Local pressure Valve closed too far" indication on N2 line, if severe

[V

ô N, pressure to HF Local pressure cylinder - no HF flow indication on N2 line o vaporizer, B-l wing

Remarks

Table 3.3.5-4 Estimated Time for an FMEA

3.4 Quantitative Methods Accident Analysis

of

Scope

Prep.

Evai.

Doc.

Simple (hr)

2-6

8-24

8-24

Complex (days)

1-3

5-15

10-20

The preceding methods were concerned with qualitative statements like: frequent, rare, unlikely, incredible, short time process disruption, several worker injuries, possible off-site deaths etc. This section seeks ways to associate risk with estimated numbers like: average time between failures of one year, 10 estimated injuries, population exposure of 10 person-rems etc. We begin with the simplest and progress to the more complex, but first consider some underlying ideas. The objective is to estimate, numerically, the probability that a system composed of many components will fail. The obvious question is, "Why don't you just estimate the failure rate of the system from operating experience?" There are three reasons: 1) the system may not exist, so newdata are not available, 2) the injuries and fatalities from the developmental learning experience are unacceptable - the risk must be known ahead of time, and 3) by designing redundancy, the probability of the system failing can be made acceptably remote; in which case system failure data cannot be collected directly. The only practical way uses part failure statistics in a system model to estimate the system's reliability.

97

Chemical arid Nuclear Accident Analysis Methods

A system model is a mathematical and symbolic representation of how the components of a system work together to perform the system's purpose. As described in Section 1.3, reliability analysis developed during World War II with the increasing complexity of military systems and the increasing need to make them reliable. Parts count methods combined the probabilities of successful component operation according to the system configuration. Markov models had early use, but are so arcane that their use is limited by mathematical complexity. As systems became increasing complex, Boolean logic was introduced in the 1960s for system modeling. Systems may be modeled to determine the combinations of successful component operations that result in system success. The same thing may be done to determine which failures of components will cause system failure. Modeling failure rather than success has two advantages: 1) the number of component combinations that will cause failure is less than the number needed for success, and 2) the arithmetic is easier because failure probabilities are generally small numbers while the probability of success is nearly 1 (many 9s before the significant digits). Boolean equations can be used to model any system; the system's reliability is calculated by factoring the equations into cutsets and substituting the probabilities for component failure. This can be done for either success or failure models. Working directly with equations is not everyone's "cup of tea1" many individuals prefer graphical to mathematical methods. Thus, symbols and appearance of the methods differ but they must represent the same Boolean equation for them to be equivalent.

3.4.1 Parts Count Perhaps the simplest way to assess the reliability of a system is to count the active parts.g The reliability estimate is the product of the number of parts and some nominal failure rate for the parts. In the design phase, two competing designs may be compared on the basis of the number of parts but several cautions are in order. If designs are compared on the basis of count, then failure rates of each type of part either must be about the same, or be adjusted for the variations. For example, the parts count of vacuum-tube and solid-state television sets (using discrete components) are approximately the same, but their reliabilities are considerably different because of the better reliability of solid state components. The other caution relates to redundant systems. Figure 3.4.1-1 shows very simple cooling systems that pump water from a tank into System A a cooling header. Header System A consists of Tank T1 a tank of water (Tl), V2 P1 an open motoroperated valve (MOV), a Fig. 3,4.1-1 Illustrative Cooling Systems

g

Active parts, i.e., parts that produce or use energy are much less reliable than those that do not - called passive. 98

Quantitative Methods of Accident Analysis

pump (PI) and a closed valve (V2). System B consists of 2 trains each of which are identical to System A, hence, System B is doubly redundant, i.e., either train may fail, but the system will still perform its designed purpose. System A has 3 active components and if the nominal failure rate is 1 E-3/demand, the failure rate of System A is 3E-3/demand. System B has 6 active components, so a superficial estimate of the system failure rate is 6E-3/demand, but because it is doubly redundant, according to equation 2.4-4, the train probabilities, if independent, should be multiplied to give System B's failure rate as: 9E-6/demand, hence, the reliability estimation by a simple parts count is grossly conservative. 3.4,2 FMEA/FMECA We previously encountered failure modes and effects (FMEA) and failure modes effects and criticality analysis (FMECA) as qualitative methods for accident analysis. These tabular methods for reliability analysis may be made quantitative by associating failure rates with the parts in a systems model to estimate the system reliability. FMEA/FMECA may be applied in design or operational phases (ANSI/IEEE Std 352-1975, MIL-STD-1543 and MIL-STD-1629A). Typical headings in the FMECA identify the system and component under analysis, failure modes, the effect of failure, an estimate of how critical apart is, the estimated probability of the failure, mitigators and possibly the support systems. The style and contents of a FMEA are flexible and depend upon the objectives of the analyst. It is interesting that NASA in their review of WASH-1400 Draft (included in WASH-1400 Final Appendix II), indicated that they had discontinued the use of fault tree analysis in favor of the FMEA. Table 342-1 Failure Modes Effects and Criticality Analysis Applied to System B of Figure 34 /-/ Component Failure mode Effect Criticality Mitigation Probability Sudden failure Water storage Loss of water No cooling water None IL-lO/hr supply supply tankTl Valve body crack Loss of fluid to Reduce flow Valve off use other MOV VI lE-10/hr header redundant train train Flow blockage No flow to header Redundant train Motor operator 1F-V inadvertent demand operation lE-Vd Pump PI Motor failure: No pumping No flow to header Redundant train bearing or short Pump failure lE-3/d bearing seize Valve body crack Loss of fluid to Reduce flow MOV V3 Valve off use other lE-10/hr header redundant train train Motor operator Flow blockage No flow to header Redundant train 2f>l/d fails to respond Gate disconnect Flow blockage 1 E-4 'd from stem

L

99


FMEA is particularly suited for root cause analysis and is quite useful for environmental qualification and aging analysis. It is extensively used in the aerospace and nuclear power industries, but seldom used in PSAs. Possibly one reason for this is that FMEA, like parts count, is not directly suitable for redundant systems such as those that occur in nuclear power plants. Table 3.4.2-1 shows a FMEA for System B in Figure 3.4.1-1. This FMEA/FMECA shows failure rates that are both demand and time dependent. Adding the demand failure rates gives a train failure rate of 5.1 E-3/demand. The sum of the time dependent failure rates is: 3E-10/hr. A standby system such as this, does not exhibit its operability until if is actuated for which the probability is needed that the train has failed since the last use Valve bodies are considered to be part of the cooling envelope and Motor operated 1 Motor operated High volume discharge valve r~ may considered to be similar to supply valve V1 pump Pt V3 1 piping. Piping characteristically leaks Water supply L before breaking, therefore it may be tankTI f expected that leakage might indicate Motor operated ] High volume Motor operated discharge valve 1 pumpP2 supply valve V2 potential fracture of the valve body. V4 If inspected monthly, the time . , - , . , . , , . „ . between inspections is 731 hours and Fl«- 3A3'} Reliability Block Diagram of Figure 3.4.1-1 the average time between inspections is 365 hours. If the distribution is exponential with an exponent much less than one, the probability of failure is the product of the failure rate and the average time since it was known to be operable: 3E-10* 365 = 1E-7, hence this type of failure may be ignored with respect to the other types to give a train failure rate of 5. lE-3/d. To complete the discussion of the FMEA analysis of System B with the redundant systems, the probabilities are multiplied, or (5.1E3/d); ~ 2.6E-Vdemand This is within a factor of 3 of the results of the parts count estimate.

3,4.3 Reliability Block Diagram (RBD). The preceding shows the care needed to understand the system logic and redundancies to model a system. Neither the parts count nor FMEA methods aid the analyst in conceptualizing the logical structure. A Reliability Block Diagram (RBD - ANSI/IEEE Std 352-1975) while laid out similarly to a flow diagram, represents the components as a series of interconnecting blocks. Components are identified by the block labeling. System B in Figure 3.4.1-1 is shown as an RBD in Figure 3.4.3-1. It is customary to draw RBDs with the source on the left and the sink on the right Even unqualified, RBDs are useful because they show the system's logic and how it can fail. "Cutset" means one combination of component failures that fail the system. It is believed to have originated as cuts across the flow in reliability block diagrams11. In Figure 3.4 3-1, a cut through

Conversation with W. Vesely 1972. 100


trains must cut through Vj or P, or V3 in combination with V2 or P2 or V4 making 9 combinations (32) with 11 cutsets for the system. Letting failure be represented by a bar over a letter (called "not"), the cutsets are: i ~

~

~ ~andJôrVâncl

'

Conditioning event - Conditions or restrictions that apply to any logic gate (for priority and inhibit gates). Undeveloped event * An event ts not developed further either because it is of insufficient consequence or because Information Is unavailable External event * An event which is normally expected to occur. INTERMEDIATE EVENT SYMBOLS

1 Intermediate event - A fault event that occurs because of one or more ' antecedent causes acting through logic gates.

_ andPôrPând GATE SYMBOLS /4orVândV2orV3andP2orV2andV O AND - Output fault if all of the input faults occur. A cutpath is a possible flow /\ OR- Output fault occurs if at least one of the iinput faults path from source to sink. ^ occurs. Exclusive Or - Output occurs if only one of the input faults occurs Considering the probabilities of Priority And - Output occurs if all of the input faults occur in a specific success (no bar) the probability of sequence (the sequence is represented by a conditioning event drawn to the right of the gate. success is: T{, and Vl andP{ and: Inhibit - Output fault ocure if one input fault occurs in the presence of an 173 andH{ ,or T,, and V2 andP2 andV4 .xx. enabling condition (the enabling condition is prepresented by a conditioning l event to the right of the gate. and HI , Upon comparison to go f ^ from failure to success one or vice TRANSFER SYMBOLS versa probability is complimented Transfer in - indicates that the tree is developed further at the occurrence of the corresponding Transfer out (on another page). and logic is reversed: AND goes OR out - Indicates that this portion of the tree must be attached to the and vice versa, as indicated by de /\ Transfer corresponding Transfer in. Morgan's theorem (Table 2.2-1). Fi 3AA 1 s mto/ The unreliability equations *- ~ >' * °fFault Tree Analy$is for an RBD are written such that the probabilities of failure of components in a train are combined in union (added probabilistically, see Equation 2.4-6) and the probabilities of trains failing are combined in intersection (multiplied, see Equation 2.4-5). Using the failure rates presented in Table 3.4.2-1, the unreliability of the redundant trains is: (1E-3 + 2E-3 + 2.1E-3) * (1E-3 + 2E-3 + 2.1E-3) = 2.6E-5/demand as obtained before. Reliability may be obtained from the unreliability by complementing the reliability (subtracting the reliability from "one") to give 0.999974. The reliability may be calculated directly, if desired, by ANDing the probabilities of successful operation of the components and ORing the success probabilities of the trains. The disadvantage of a direct reliability calculation is the large number of "9's" involved in the probabilities of success. RBDs are a very useful method for analyzing a simple system, but complex systems are usually analyzed by fault tree analysis which uses special symbols for the operations of union and intersection. An advantage of RBD over fault tree analysis is that the RBD logic diagram resembles a flow diagram or a piping and instrumentation diagram (P&ID) and is more easily understood without training in fault tree analysis. 3.4.4 Fault Tree Analysis This section describes the most commonly used method for complex systems analysis - fault tree analysis. The previous section introduced cutsets as physically cutting through an RBD, here, cutsets are presented mathematically. The symbols of fault trees are introduced and a heuristic 101


demonstration, based on von Misesian probability, shows the transformation of logic equations to probability equations. This is followed by rules for fault tree construction and a demonstration of transforming a fault to a success tree. 3.4.4.1 Fault Tree Symbols

Exhaust valve

~—-—

Head gasket

Piston ring 1 Figure 3.4.4-1 summarizes conventional fault tree VPteton ring 2 1 symbols. The many symbols are daunting, but remember Piston f that the computer only performs AND (Boolean multiplication) and OR (Boolean addition) operations. All else are combinations of these. Under the primary event symbols, the circle represents a component failure for which a description and Fig. 3.4.4-2 Sketch of an Internal failure-on-demand or failure frequency data* is provided. Combustion Engine The oval symbol represents a probability or failure rate. A diamond is an event that is not developed because the preparer did not know what to do or thought it insignificant. A house-top is an expected occurrence (probability of one). Rectangles identify and explain gates. The gate symbols are the AND gate which has a flat bottom and is true if all inputs (logic into the bottom of the gate) are true. The OR gate has a curved bottom and is true if one or more inputs are true. The Exclusive OR is true if only one input is true. Priority AND requires all inputs but in a given sequence. Inhibit acts like a gate. It is actuated by a side signal to pass the bottom signal. The transfer triangles are very useful for connecting one modular fault tree to another for size control.

o

3.4.4.2 From Logic to Probability A simple example of fault tree analysis applied to an internal combustion engine (Figure 3.4.4-2) is the Figure 3.4.4-3 fault tree diagram of how the undesired event: "Low Cylinder Compression" may occur. The Boolean equation of this fault tree is in the caption of Figure 3.4.4-3. Let the occurrence of these events be represented by a 7, non-occurrence by 0, and consider that there may be a long history of occurrences with this engine. Several sets of occurrences (trials) are

1

For an expanded discussion of the symbol meanings, refer to the Fault Tree Handbook, NUREG-0492. J

It is necessary to check units to be sure they make sense. Fault trees are often associated with event trees in which only the initiator has the units of frequency and the fault trees are dimensionless probability. This dimensionless is achieved by failure rates being paired with a mission time.

102


depicted in Table 3,4.4-1. After this history, the number of failures may be summed to find that the top event (LCC) times from the various occurred N,LCC component failures combinations (equation 3.4.4-1). Dividing equation 3.4.4-1 by the total number of trials T and letting T go to infinity, probability in the von Misesian sense results in equation 3.4.4-2. It is important to note that the symbols + and * in this equation represent the operations of union and intersection using the rules of combining probability not ordinary algebra (Section 2.1). Thus, the conversion from a logical repreFig. 3,4.4-3 Fault Tree of Engine sentation to a probability representation follows naturally from superposition and the von Misesian definition of probability. Simply replace the component identifier by its failure probability and combine probabilities according to the logical operations.

3.4.4.3 Cutsets

Table 3.4.4-1 Hypothetical Engine Operating Experience SP Trial LCC HG EV IV PR1 PR2 0 0 | 1 0 0 0 0 I 9. 0 1 0 0 0 0 0 n L_ 0 0 1 0 0 0 0 0 1 0 0 0 1 n 4 0 0

p

Two-state (off-on) logic being discussed and specifically, fault trees, may be represented by a Boolean equation. A fault tree (or other logical diagram) may be drawn in different 1 0 1 1 0 0 0 0 T-l ways that are equivalent if the equation of the 1 0 1 1 0 0 i i T logical diagram is the same. To show they are Total NLCC NHG NEV NIV NSP Np NpRl N ^PR2 the same, it may be necessary to change the form of the equation by (3.4.4-1) factoring and rearranging p p p +p +(p +p + + + -P rP according to the rules of Boolean LCC r HG r EV rlV rSP rNP \rPnPRl ' r'" PR2> (3.4.4-2) algebra presented in Table 2.1-1. Top event ^ (3.4.4-3) A particularly powerful factorization of a Boolean equation is the sum of products form (equation 3.4.4-3). This is the mincut (minimal cutset) representation (Section 2,2) - the smallest combination of component failures that will result in the top event. By the definition, a minimal cutset is the collection of those events that produce the top event (no extras), although there may be many different collections. The combination is the smallest unique collection of components which if they all failed, produce the top event. If any components in the cutset do not fail then the top event will not occur - at least by that cutset. Any fault tree consists of a finite number of minimal cutsets. One-component minimal cutsets, if there are any, represent single components whose failure alone causes the top event to

103


occur. Two-component minimal cutsets are double failures which cause the top event io occur. N-component minimal cutsets, are the n components whose collective failure causes the top event to occur. In equation 3.4.4-3, a mincut is one of the products; whose sum constitutes all the ways of failing the mincuts.k For an w-component minimal cutset, all n components in the cutset must fail in order for the top event to occur. The minimal cutset expression for the top event can be written in the general form: T - M, + M2 + • - • + Mk, where T is the top event and M} are the minimal cutsets. Each minimal cutset consists of a combination of specific component failures, hence, the general «~component minimal cut can be expressed as: M2 = X1*X2__*Xn, where X,, X,, ... are basic component failures. An example of a top event expression is: T= A+ B*C, where A, B, and C are component failures. This top event consists of a one-component minimal cutset (A) and a two-componentminimal cutset (B*C). The minimal cutsets are unique to the top event and independent of other ways the fault tree may be drawn. Top-Down Solution To determine the minimal cutsets of a fault tree, the tree is first translated into its equivalent Boolean equations and then either the "top-down" or "bottom-up" substitution method is used. The methods are straightforward and involve substituting and expanding Boolean expressions. Two Boolean laws, the distributive law and the law of absorption (Table 2.1-1), are used to remove superfluous items. Consider the example fault tree (Figure 3.4.4-4); the Boolean equations taken, gate at a time. are: T = E1*E2, El - A+E3, E3 = B+C, E2 = C+E4, E4=A*B. Start with the T-equation, substitute, and expand until the minimal cutset expression for the top event is obtained. Substituting for El and E2 gives: T=(A+E3)*(C+E4) = (A*C)+(E3*C)+(E4*A)+(E3*E4). Substituting for E3: T = A*C +(B+C)*C + E4*A +(B+C)*E4 = A*C + B*C + C*C + E4*A + E4*B + E4*C. Using idempotency (C*C=C) gives T=A*C +B*C+C +E4*A+ E4 *B+E4*C. But A*C +B*C + C + E4*C - C hence r j the law of absorption produces: T = C + E4*A + E4*B. Q Finally, substituting for E4 and applying the law of | _*? ~i f ~p2 ! l absorption twice: T=C+ (A*B)*A+ (A*B)* B =C+A*B ry-* p. Thus, the fault tree of Figure 3.4.4-4 is represented in mincut ,xJ=i=U= - -— - c E4 form as: T =C+A*B and by fault tree as Figure 3.4.4-5 which shows C^,) i E3 the remarkable simplification and reduction provided by the mincut Q Q form. This shows that the top event, T, consists of a single f^\ f'c\ & Q» v component failure, C, and a doubly-redundant failure. Fig. 3.4,4-4 Example Fault Tree k

The term "min" is readily understood when Boolean algebraic reduction is applied to the logic equation, because terms like A + A*C collapse to A, thereby affording considerable simplification. The reason for this is if A causes failure, then additional failures are superfluous.

104


Bottom-Up Solution The bottom-up method uses the same substitution and expansion techniques, except that now, the operation begins at the bottom of the tree and proceeds up. Equations containing only basic failures are successively substituted for higher faults. The bottom-up approach can be more laborious and time-consuming; however, the minimaj cutsets are now r '} obtained for every intermediate fault as well as the top event. /~\ Returning to Figure 3.4.4-4: T = E1*E2, EJ = A+E3, E3 = B+C, E2 = _ U , C+E4, E4=A *B. Because E4 has only basic events, substitute it into E2 to obtain: i C A*B '• E2 =C + A B, The minimal cutsets of £2 are thus C and A*B. E3 is already in Q reduced form having minimal cutsets B and C. Substituting El = A+B+C, hence >"''«'• El has three minimal cutsets A, B, and C. Finally, substituting the expressions for £1 and E2 into the equation for T, expanding and applying the absorption law gives: 'f " ' ' _ " I = (A+B+C) (C+A*B) =A*C+A*A*B+ B*C+B*A*B+C*C+C*A*B = A*C '"TWO"* +A*fi+ B*C +A*B +C+A*B*C = C+A*B - the same as was obtained previously Figure 3.4.4-4 by the top-down method.

3.4.4,4 Considerations in Fault Tree Construction. Top Event A fault tree may either stand alone or be coupled to an event tree to quantify a nodal probability. The top event in either case is the objective of performing the analysis. If the objective is the reliability of a system under specific conditions - then that is the top event. If it is to quantify a node of an event tree the top event title is that of that particular node subject to the conditions imposed by the preceding modes. Clearly and uniquely specify the top event to the precise requirements without overspecification which might exclude important failure modes. Even if constructed by different analysts, the top event specification should produce trees that have the same Boolean equation. The fault tree identifies component failures that cause the top event. Systems may be required to respond in different ways to different accidents, suggesting a general top event for a general purpose fault tree that adapts to specific system configurations. This may result in ambiguity in the top event definition and difficulty in construction. It is better and easier to precisely specify the top event for one system configuration, construct its tree, and do the same for each system configuration. Such editing of trees is greatly facilitated by the computer. An example of a multipurpose system is a reactor's low pressure coolant injection system which uses one out of four (1/4) pumps for a small LOCA, and three-out-of-four pumps for a large LOCA (3/4). The top event for the small LOCA might be: "none of four LPCI pumps fail to start within five minutes and deliver rated flow for at least two hours following a small LOCA." The large LOCA top event might be: "more than two-out-of-four LPCI pumps fail to start within five minutes and deliver rated flow for at least two hours. Such a top event specifies failure in physical and temporal terms.

105


System Definition. Before the analyst begins fault tree construction, it is necessary to document and understand: System design, Causes of top event failure including substructure and components, Support necessary for operation, Environment, Components failure modes, and Test and maintenance practices. Documentation of the system design and operating data, analytical assumptions and constraints used in the analysis in a notebook becomes part of the QA record. However, it is useful to have documents analyses and records as computer files for handling the voluminous data reporting and presenting the results of the work. It provides. A risk assessment analyses systems at two levels. The first level defines the functions the system must perform to respond successfully to an accident. The second level identifies the hardware for the systems use. The hardware identification (in the top event statement) describes minimum system operability and system boundaries (interfaces). Experience shows that the interfaces between a frontline system and its support systems are important to the system evaluation and require a formal search to document the interactions. Such is facilitated by a failure modes and effect analysis (FMEA). Table 3.4.4-2 is an example of an interaction FMEA for the interface and support requirements for system operation. Failure Modes and Effects Analysis (FMEA) A failure modes and effects analysis delineates components, their interactions with each other, and the effects of their failures on their system. A key element of fault tree analysis is the identification of related fault events that can contribute to the top event. For a quantitative evaluation, the failure modes must be clearly defined and related to a numerical database. Component failure modes should be realistically and consistently postulated within the context of system operational requirements and environmental factors. All component fault events can be described by one of three failure characteristics: 1. Failure on Demand. Certain components are required to start, change state, or perform a particular function at a particular time. Failure to do so is a "failure on demand." 2. Standby Failure. Some systems or components are normally in standby, but must operate when demanded. Because they are on standby, their failed state will be unknown unless it is caught by testing. This is "standby failure." 3. Operational Failure. A system or component may fail in normal operation or may start but fail to continue for the required time. This is an "operational failure."

106


Front-line System Div. Comp.

Table 3.4.4-2 Example Format for an Auxiliary Feedwater System Interaction FMEA Support system System

Div. Comp.

Failure mode Fail open

A

MDP-IA AC Power A

B

MDP-1B AC Power B

A.

MDP-tA AC Power A

Breaker A1131 Breaker A1132 Bus Eli

B

MOP- IB AC Power B

BusF12

A

MDP-IA HVAC

A

B

MDP-1B HVAC

B

A

MDP-IA ESWP

A

Rx cooler 3A Rx cooler 3B Oil cooler Loss of service S31 water

B

MDP-1B ESWP

B

Oil cooler S32

A

MDP-1A DC Power A

BusAlSl

B

MDP-1B DC Power B

Bus A 132

Low voltage

Failure effect

Detection Diagnosis

Concurrent At pump Pump failure to start test operability or run CFSR only

Treat as part of local pumping failure

CFSR motor failure

Partial failure noted for future reference

Prompt

Control room monitors ESG EF1 1 voltage alarmed No heat Pump motor Shift walk No warning removal burnout in 3- around for local 10 continuous faults service hours

Low voltage

Comments

Pump motor At pump Local lube oil burnout in 1-3 test temperature CSH gage, none in control room

Precludes auto Prompt or manual start, no local effect on already running pump

Control room monitors DC bus voltage many lamps out in control room

AC and SWS support systems of HVAC monitored but not HX ESW'S header and pumps monitored but not lube oil coolers, local manual valve alignment checked in maintenance procedure xx but not periodic walk around. Effect of DC power loss on AC not Evaluated here; local motor controller latches on, needs DC to trip or close

In addition, test and maintenance activities can contribute significantly to unavailability by components being out of service for test or maintenance. The amount of unavailability from this cause depends on the frequency and the duration of the test or maintenance act. Three general types of testing that may make systems unavailability are: 1. Tests of the system control logic to ensure proper response to appropriate initiating signals. 2. System flow and operability tests of components such as pumps and valves. 3. System tests performed after discovering the unavailability of a complementary safety system, generally referred to as tests after failure. Testing schemes generally affect complete subsystems; hence, consideration of each hardware element is unnecessary. Tests of redundant portions of a system are particularly important, and may be constrained by the technical specifications which must be reflected in the fault tree. Testing may require the reconfiguration of systems for the test, which may prevent the performance of their designed function. In this case, other members of the redundancy must be available, but may fail. Failure to restore a system after test significantly increases the risk. 107


Maintenance, whether routine or unscheduled contributes to system unavailability. The frequency and duration can be obtained from the maintenance procedures. Take care that outages associated with preventive maintenance are not already included in the time intervals assigned to testing. Unscheduled maintenance activities are caused by essential equipment failures. Because these activities are not scheduled, the frequency and the mean duration of maintenance is based on statistics from experience. Human factors, discussed in Section 4.2, enter a fault tree in the same manner as a component failure. The failure of manual actions, that prevent or mitigate an accident, are treated the same as hardware failures. The human error failure probability is conditioned by performance shaping factors imposed by stress, training and the environment. Human errors may be dependent on the specific accident sequence displayed in the event tree, and, for that reason, may be included in the event tree. This requires the human-factors specialist to consider the context of the error in terms of stress, operator training in response to the accident, diagnostic patterns, environmental, and other performance-shaping factors. 3,4.4.5 Fault Tree Construction Rules Fault Tree Hierarchy Initially, a system's hierarchy is identified for subsystems, sub-subsystems and so on to the components for which data must be found. The top event specifies system failure; subsystems required for operation of the system in the mode specified are input to the top event's OR gate. Redundancy is represented by the redundant systems inputting an AND gate. This process of grouping subsystems under OR gates, if they can individually fail a function, or under AND gates if concurrent failures are necessary, is continued to the component or support system level until the tree is completed. This process grades the hierarchy from top to bottom, down the fault tree. Trees can grow geometrically to become impractically large. Furthermore, very large trees are difficult to understand and review. The fault tree triangle linking symbol surmounts this problem by breaking a large tree into linked small trees. Subsystems that are logically identical may be represented by the same subtree but with different component identifiers for each of the subsystems represented. A fault tree may diagram a system to the component level, but including support systems in the tree would add complexity and size. This is circumvented with linking triangles to connect the fault trees of the support systems. Since the support system may support several systems, this technique minimizes the need for duplicate fault trees. Label the Gates Gates look alike; the are only distinguished by the gate label. Each event box is labeled to fully describe the postulated fault according to the what and when about the event. The precise statement enhances the analysis by: focusing on the event, and aiding the fault tree review.

108


Complete the Gates Complete all gate inputs. Beginning a new gate before completing a previous gate leads to confusion and incompleteness. These rules are made concrete by an example of fault tree analysis. 3.4.4.6 Example of Fault Tree Construction

^ Valve E *o r-*

—P 1 ..+f

}

t

f.

Valve A

Valve B

--->o itU

'

5. .

Valve D

Pump Figure 3.4.4-6 presents a flow diagram of a Fig. 3.4,4-6 Simple injection system simplified emergency cooling injection system. It is activated by a safety injection signal (SIS) which sends control signals along the dotted lines as shown. The top event selected for the fault tree

Insufficient flow to valve "S"

A1=A+B+B1 Bl =C1*C2 C1=C+B+D1 C2 = D+B+D1 D1 = E+B+E1 El = F1+F2 Fl = F+G+B F2 = H+B Substituting, El = (F+G+B) + (H+B) Dl = E+B+(F+G+B)+(H+B) C2 = D+B+E+B+(F+G+B)+{H+B) Cl = C+B+E+B+(F+G+B1+(H+B) Bl = [C+B+E+B+(F+G+B)+(H +B)]*[(D+B+ E+B+(F+G+B)+(H+B) Al = A+B+[C+B+E+B+(F+G+B) + (H+B)] *[(D+B+E+B+(F+G+B)+(H+B }] Simplifying, Al = A+B+(C+B+E+B+F+G+H+B)* (D+B + E +F+G+ H) Multiplying, Al= A+B+C*D+C*B+C*E+C*F+C*G+C*H +B*D+B*B+B*E+B*F+B*G+B*H+E*D +E*B+ E*E+ E*F+E*G+E*H+ F*C+F* B+F*E+F*G+F*H+G*D+G*B+G*E+G* F+G*G+G*H+H*D+H*B+H*E+H*F + H*G+H*H Using identity: X*X=X, Al =A+B+C*D+C*B+C*E+C*F+C*G+ C*H+B*D+B+B*E+B*F+B*G+ B*H+E*D+E*B+E+E*F+ E*G+ E*H+F*D+F*B+F*E+F+F*G+F *H+G*D+G*B+G*E+G*F+G+G *H+H*D+H*B+H*E+ H*F + H*G + H Using identity: X+(X*Y}=X, A 1 = A + B + E + F + G + H+ C*D

Insuftclent flow to valve "C"

Fig. 3.4.4-8 Boolean Reduction of "Failure to Inject" Fault Tree '»

B

Fig. 3.4.4-7 Failure to Inject Fault Tree

109


(Figure 3.4.4-7) is "Failure to Deliver Sufficient Flow through Valve D"; the analyst starts with valve I) and asks how the top event could occur? Valve D could fail to open (A) or valve D may not receive a SIS (B) which, according to Figure 3.4.4-7, the analyst does not think credible, or valve D may not get flow from valve B and valve C. This process proceeds down through the system hierarchy. Notice that the labels on the gates from A to F indicate this progression. A note of caution, however; this tree is not concisely drawn as will be shown in the algebraic reduction of the tree. The progression into the hierarchy is not from complex to simple, because these systems are essentially of the same level of complexity. Figure 3.4.4-8 shows the algebraic reduction of the fault tree using the rules of Table 2.1-1. The simplicity of the final result is the mincut representation (sum of products - Section 2.2) depicted as a fault tree in Figure 3.4.4-9. If the single double, and so on to higher redundancy components had been identified, the complex and awkward tree of Figure 3.4.4-8 would have been avoided. Some systems are so complex that this cannot be done by observation, but computer analysis will show simplicities if they exist.

3.4.4.7 Success Tree Using de Morgan's theorem (Table 2.1-1), the fault tree in Figure 3.4.4-9 is converted into the success tree shown in Figure 3.4.4-10. Notice that the effect of the theorem is to reverse the logic: "AND" gates become "OR" gates and vice versa; failure becomes success and vice versa. Success trees, by definition, are success oriented. Some analysts claim that a success tree is a state of mind and that a true success tree cannot be adapted from a fault tree by de Morgan's theorem but must be built from "scratch" to involve the psychology of success rather than of failure.

Fig. 3.4.4-10 Success Tree Transformation of Figure. 3.4.4-9 Fault Tree

Fig. 3.4.4-9 Fault Tree from the Mincut Representation of Figure 3.4.4-8 Fault Tree

110


3.4.4.8 Preparing Fault Trees for Evaluation A fault tree is a graphical form of a Boolean equation, but the probability of the top event (and lesser events) can be found by substituting failure rates and probabilities for these two-state events. The graphical fault tree is prepared for computer or manual evaluation by "pruning" it of less significant events to focus on more significant events. Even pruned, the tree may be so large that it is intractable and needs division into subtrees for separate evaluations. If this is done, care must be taken to insure that no information is lost such as interconnections between subtrees. Before quantitative evaluation, the events must be coded with an unique identifier. A systematic and orderly identification scheme minimizes the possibility of ambiguity or multiple identifier for the same event. Some fault tree coding schemes use eight-character event identifiers; others use 16-character identifiers. A good coding scheme mnemonically Operation Damage identifies the system in which the component is State D TBTc located, the component type, the specific component identifier, and the failure mode. More complex identifiers give additional information, such as the component location that is needed for common cause Success! searches. Graphical fault tree codes (e.g., IRRAS) supplement the coding with text describing the event.

3.4.5 Event Trees Failure

3,4,5,1 Event Tree Construction Event trees are constructed using the following steps:

F1 Step I - Initiator Selection 8- 3-4.5-1 Event Tree Scenario Depiction An event tree is a model of the process' The left side connects to the initiator, the right side to ... ... process damage states, the top oar gives the systems response to an accident initiator. The initiators are in the order that they enter the scenario. The nodes found from a Study of the plant's processes, its (dots) are entry points for the branching probabilities Operating history, and accidents in related facilities, that may be determined from fault tree analysis or Collectively these initiators and their analyses define from a database. Success is indicated by the path going up at a the risk envelope of the plant (Figure 1.4.2-2). «**••*«««is b>' *™« >

8o

Ml

o

•a £ es

1

E

fc«

03 t> 60

-H 1 U

s js

X

X X X X X X

Non-nuclear instrumentation power

tot!

Low pressure spray pump

E 1QO) containing burnable neutron poisons, and by varying the flow rate through the reactor for normal, fine control. Two recirculation loops using variable speed recirculation pumps inject water into the jet pumps inside of the reactor vessel to increase the flow rate by several times over that in the recirculation loops. The steam bubble formation reduces the moderator density and

211

Analyzing Nuclear Reactor Safety Systems

Wet well - water Fig. 6.1-2 Sketch of a Boiling Water Reactor(BWR) The core heats water to steam which is dried, sent to the turbine that powers the generator sending electricity to the network.. Steam depleted of its energy is condensed and returned to the reactor vessel by feedwater pumps. Water is circulated in the reactor vessel by jet pumps which are powered by water circulated by the primary cooling pumps. The control rod drive mechanism (CRDM) is located in the bottom (away from the steam). In case of a LOCA, the automatic depressurization system discharges into the wet well to reduce the pressure so the high pressure safety injection (HPSI), low pressure safety injection (LPSI), and the low pressure cooling system can operate. The standby liquid control system injects borated water to help shutdown the reactor

consequently the reactivity. Higher flow through the core reduces the bubble density and increases the reactivity. If a rapid shutdown (scram) is required, the control rods are inserted in from the bottom by hydraulic drives. Each control rod drive is separate and is actuated by deenergizing a solenoid valve to release high pressure accumulator water to drive the pistons and insert the rods. In case of scram accumulator failure, reactor pressure will insert the rods. This system is backed-up by a Standby Liquid Control System (SLCS) that injects sodium pentaborate into the moderator using a positive displacement pump (shown as a piston pump). Steam that originates in the core of a BWR, unlike the primary coolant in a PWR, exits the containment. The closing of the MSIVs isolates the radioactivity from the environment but when this is done, normal heat removal is not possible. The Residual Heat Removal (RHR) system 212

Nuclear Power Reactors Table 6.1-4 List ofBWR Transient Initiating Events (adapted from NUREG-2300) 1 , Biectric load rejection 2. Electric load rejection with turbine bypass valve failure 4. Turbine trip with turbine bypass valve failure 3. Turbine trip 5. Maia steam isolation valve (MSIV) closure 6. Inadvertent closure of one MSIV 3. Loss of normal condenser vacuum 7. Partial MSIV closure 10. Pressure regulator fails closed 9, Pressure regulator fails open 12. Turbine bypass fails open 11. Inadvertent opening of a safety/relief valve (stuck) 13. Turbine bypass or control valves cause increase in pressure 14. Recirculation control failure increasing flow 16. Trip of one recirculation pump 15, Recirculation control failure decreasing flow 18. Abnormal startup of idle recirculation pump 17. Trip of all recirculation pumps 20. Feedwater increasing flow at power 19, Recirculation pump seizure 22. Loss of all feedwater flow 21 . Loss of feed water heater 24. Feedwater iow flow 23. Trip of one feedwater pump (or condensate pump) 26. High feedwater flow during startup or shutdown 25. Low feedwater flow daring startup or shutdown 28. High flux due to rod withdrawal at startup 27. Rod withdrawal at power 30. Detected fault in reactor protection system 29. Inadvertent insertion of control rod or rods 32. Loss of auxiliary power (loss of auxiliary transformer) 3 1 . Loss of offsite power 34. Scram due to plant occurrences 33. Inadvertent startup of HPCI/HPCS 36. Manual scram; no out of tolerance condition 35. Spurious trip via instrumentation, RPS fault

provides another path for removing the residual heat. Initially in an accident, the reactor will be near operating pressure and the High Pressure Core Spray (HPSI) is the only way to inject cooling water but not at a high flow rate. The HPSI takes water from the suppression pool or from the condensate storage tank. An alternative is to trip the Automatic Depressurization System (ADS) and release the steam by way of downcomers below the water level in the suppression pool. This condenses the steam but heats the suppression pool water which is cooled by circulation through heat exchangers (a function of the RHR not shown in the Figure). As the pressure drops, the Low Pressure Core Spray begins and pumps water from the suppression pool through a heat exchanger and sprays the reactor core. During an accident, steam accumulates in the containment, hence, another mode of the RHR is to circulate suppression pool water through heat exchangers and spray the inside of the containment with cooling water. Table 6.1-4 lists BWR transient initiating events; Table 6.1 -5 lists BWR frontline systems.

6.1.4 Advanced Light Water Reactors Sections 6.1.2 and 6.1.3 describe first generation reactors designed in the 1950s. These designs began with requirements for producing power - auxiliary systems were added as needed. This incremental approach led to: complexity, high initial and operating costs, regulatory complexity, and safety concerns, especially following the TMI-2 accident. The first generation of power reactors was designed by the vendors and offered to the

213


Table 6.1-5 Typical BWR Frontline Systems LOCA Frontline system Render reactor subcritical Remove core decay heat

Function Reactor protection system

Prevent containment overpressure

Suppression pool Residual heat removal system Containment spray system

Scrub radioactive materials

Suppression pool Containment spray system

Main teedwater system Low pressure coolant injection system Low pressure core spray system Automatic pressure relief system High pressure coolant injection system Reactor core isolation system

Transients Frontline system Function Render reactor Reactor protection system subcritical Standby liquid control system Remove core Power conversion system decay heat High pressure core spray system ffigh pressure coolant injection system Low pressure core spray system Low pressure coolant injection system Reactor core isolation cooling system Feedwater coolant injection Standby coolant supply system Isolation condensers Control rod drive system Condensate pumps Prevent reactor Safety relief valves coolant Power conversion system overpressure Isolation condenser Prevent Residual heat removal system Shutdown containment cooling system Containment spray system overpressure Scrub radioactive Suppression pool materials Containment spray system

utilities. With approximately 1,000 reactoryears of experience, the utilities, led by EPRIreversed this process by specifying the attributes for the next generation of plants. Requirements are given in Table 6.1-6. By inference, this table criticizes the first generation reactors.

Core damage frequency < lE-5/reactor-year,

6.1.4.1 Westinghouse AP-600

Greater than 87% availability averaged on the plant lifetime

Table 6.1-6 Attributes for Second-Generation Reactors

Severe events with a frequency of > 1 E-6/reactor-year to result in
3.1E-4

X

LOCA(1,66"<EX4") LOCA(4"-FN.MO where the semicolon designates enter. Notice these equations are linked with BLACKOUT being the top event. This completes the preparation of FTAP input; selection 6 exits FTAPlus to return to Fig. 6.4-2 Procedure for Using FTAPSUIT the FTAPSUIT menu (Figure 6.4-3). Figure 6.4-2 shows file FN.FI was created. This is an ASCII file which can be edited, if needed, with a text editor. The next step is to run FTAP using selection 2 from the FTAPSUIT menu (Figure 6.4-3). It asks you to enter the file name that you assigned. Do not give an extender. A "successful completion" sign indicates proper FTAP execution. At this point, the cutsets have been found and can be seen by reading file FN.FO with a text editor. While this qualitative analysis is useful, usually

h

In Windows 3.1, go to the file manager click on the hard drive, click on file, click on "create directory" type FTAPSUIT, and copy the "A" drive to this directory. In Windows 95 go to the explorer, click on hard drive, right click and choose "make folder" and copy disk to it.

240

Example: Analyzing an Emergency Electric Power System

Master Program for FTA Associates Codes 1. Prepare Input for FTAP 2. RunFTAP 3. Prepare Input for POSTPROCESSOR 4. Run POSTPROCESSOR 5. Run BUILD 6. Prepare Input for IMPORTANCE 7. Run IMPORTANCE 8. Run MONTE H. Help File Q. Quit

FTA Associates FTAPlus Main Menu

1: 2: 3: 4: 5: 6:

Provide Title for FT AP Provide File Name Input FTAP Tree Logic and Save Input Data for POSTPROCESSOR and Save Input FT Data for IMPORTANCE and Save Leave the Analysis Session Select the Number Identifying Your Job Fig, 6.4-4 FTAPlus Menu

Input designation of Task, Press ENTER

FTA Associates Postprocessor Input

Fig, 6,4-3 Menu for FTAPSUIT

a quantitative analysis is required. Figure 6.42 shows that the qualitative analysis can be used asis by using BUILD via file FN.PCH or POSTPROCESS to modify the operation and indicate conditional probabilities. The postprocessor reads the punch file from FTAP and generates an output file in a format which can be read by BUILD. It can execute commands not found in FTAP. Features of the postprocessor include: * »

« •

1: Eliminate Complemented Events (NOCMPL) 2: Print MinCuts in FTAP Format (PRTDNF) 3: Same as 2 and Boole Equa. for Top Event (FRMBLK) 4: SORT 5: Mutually Exclusive Input (MEX) 6: Substitute CutSets for Dependencies (SUB) 7: Exit Menu

Conducting common cause and Select the Number Identifying Your Job dependent event analysis Fig. 6,4-5 Postprocessor Menu Dropping complemented events and performing the subsequent minimization Generating block files (i.e., a set of Boolean equations) for subsystems Eliminating min cut sets with mutually exclusive events.

Selection 3 from the FTAPSUIT menu (Figure 6.4-3) runs FTAPlus to prepare input for the postprocessor (Figure 6.4-5). To print the contents of the block file, the postprocessor input must contain either the command PRTDNF or FRMBLK (selections 2 and 3 respectively). The command PRTDNF (print equation in disjunctive normal form) allows you to display the contents of a punch file in readable form. FRMBLK (form block) is required to generate an FTAP input file. The 241


command NOCMPL drops complemented events (i.e., assumes that they are true) and performs the subsequent minimization. The command SORT sorts cutsets according to order. It is necessary to sort the punch file to run IMPORTANCE if cutsets are not listed according to order in the punch file. (This occurs when probabilistically culling in FTAP using the IMPORT instruction.) MEX and SUB are optional commands. MEX command must precede the SUB command. The MEX command sets to false, basic events that are pairwise mutually exclusive. For the SUB command, the user identifies sets of basic events within cutsets (original sets) that are to be replaced by another set of basic events (substituted sets). The SUB command accounts for basic events within cutsets that have either a common cause or statistical dependency. After selecting the MEX command (selection 5) the comma delimited input consists of groups of basic events that are pairwise mutually exclusive. To extend the group to the next and subsequent lines, the first field must be blank. Up to 100 names per group are allowed with a new group starting when a non-blank character is encountered in the first field. The number of pairs that are mutually exclusive is: n!/[(n-2)! *2!], where n is the number of basic events in the group. An example for the plant blackout fault tree is: DG-A-M,DG-B~M,DG-C-M; (where ";" means enter). Selection 6 (Figure 6.4-5) executes the SUB command. The comma-delimited input alternates between the cutset to be replaced and the cutset replacing it. For example for the plant blackout problem, the input is: DG-A,DG-B,DG-C;DG-A,DG-B/A,DG-C/A&B;DG-A,DG-B;DGA,DG-B/A;DG-A,DG-C;DG-A,DG-C/A;DG-B,DG-C;DG-B,DG-C/B. The actual input to BUILD alternates lines with * and ** to identify lines to be replaced with replacing lines, but this bookkeeping is done automatically by FTAPlus. The original set of basic events and the substituted set cannot exceed 99 basic events. The SUB command completes the postprocessor input. Select 7 to exit the postprocessor menu and 6 to exit FTAPlus for the FTAPSUIT menu. Select 4 from this menu and POST (postprocessor) begins by requesting the data input file name (e.g., dg.pi - prepared by FTAPlus), the punch file name (e.g., dg.pch), the block file name (e.g. dg.blk) and the name to be assigned to the new punch file (e.g., dgn.pch). Two outputs are produced: FN.BLK and FNN.PCH. Select 5 from the FTAPSUIT menu and BUILD starts by requesting the punch file name (e.g., dgn.pch or dg.pch depending on whether you want to run the original fault tree or the postprocessed fault tree. It requests the name to be given the importance input file (e.g., dg.ii) to select the type of input. Option 5 is pure probability, option 1 is failure rate. BUILD generates file FN.II for editing. Selection 6 goes to FTAPlus from which menu 5 is selected, to provide the information needed for IMPORT. This program presents event names as given in FTAP and POST and requests failure rates or probabilities (e-format), uncertainty (f-format), and an event description. Each time this set is given, it presents the next event name until all events are specified. Then it returns to the main FTAPlus menu to be exited by selecting 6 to go to the FTAPSUIT menu. Selection 7 causes IMPORT (importance) to start by requesting the name of the input file FN.II (e.g., dgn.ii). The importance output is contained in the FN.IO file. The output needed by MONTE is FN.MI. Selection 8 from the FTAPSUIT menu runs MONTE (Monte Carlo). It requests the name of the input file, FN.MI (e.g., dgn.mi). The Monte Carlo analysis is contained in file FN.MO. 242

Problems

For examples of the output files refer to Section 7.4 for the example of analyzing a fault tree for a chemical process vessel rupture.

6.5 Summary Previously, discussions have been on the theory and practices of PSA, this chapter focuses on the analysis of nuclear power plant systems. It began by discussing the first generation of light water cooled and moderated nuclear power: BWRs and PWRs. The major systems were presented with emphasis on safety systems. Safety concerns with the first generation of LWRs are addressed in the design of the advanced reactors of which a few have been constructed in Japan. Advanced reactors that are discussed are the Westinghouse AP-600, ABB System 80+, ABB's PIUS, and General Electee's ABWR and SBWR. The two major accidents of nuclear power plant are described: TMI-2 and Chernobyl the latter of which caused a few radiation deaths and many more deaths from conventional causes. The next section discussed the preparation of nuclear PSAs: management and organization of a PSA team, preliminary information needs, identifying the initiators, event tree focus of the analysis, database preparation, construction of event trees and fault trees, determination of the plant damage states, and the consequences of an accident, The chapter concludes with the example: analyzing an emergency electric power system using FTAP and supporting codes that are provided on a distribution disk with this book. FTAP and supporting codes were written for main frame computers. To facilitate the bookkeeping on a PC, FTAPSUIT and FTAPlus are provided and the reader is walked through the analysis of the emergency electric power system to obtain point probabilities, confidence limits, and importances.

6.6 Problems 1. A critical assembly is a split bed on which fissionable material used to mock up up a separated reactor core that is stacked half on each half. One half is on roller guides so that the two halves may be quickly pulled apart if the neutron multiplication gets too high. Use the Preliminary Hazards Analysis method described in section 3.2.1 to identify the possible accidents that may occur and the qualitative probabilities and consequences. List the initiators in a matrix to systematically investigate the whole process. Don't forget human error. 2. Removing decay heat has been the "Achilles Heel" of nuclear power. The designs shown in this section use active methods to remove the heat, (a) Sketch and discuss a design that removes the heat passively, (b) It would seem that the energy in the decay heat could be used for its own removal. Sketch and discuss a design that uses this property to remove the decay heat. 3. When Hamlet said to Horatio, "there are many things twixt heaven and earth not conceived of in your philosophy," was he complete in the scope of his coverage? If so can this approach be used for completeness in identifying all the possible accidents? 4. In the WASH-1400 analyses of nuclear power accidents, it was calculated that it is possible to overpressure and rupture the containment. Discuss whether this is better or worse than a pressure relief that releases radioactivity but prevents the pressure from exceeding the rupture

243


point. Spent fuel reprocessing plants are designed to release filtered and processed gases. Typically the final filters are large containers of sand or HEPA (high efficiency participate air) filters. Discuss filtered containment with consideration for possible failure modes of the filter. 5. Early BWRs used an isolation condenser, although such is not specific to the direct cycle. This device removes decay heat by steam flow through a heat exchanger the other side of which is water vented to the atmosphere. Discuss the relative merits of such a boiler.

244

Chapter 7 Analyzing Chemical Process Safety Systems

As the previous chapter discussed nuclear power reactor operation and how to perform a PSA on it, this chapter attempts to apply a similar framework to chemical processing. The problem is the diversity of chemical processing that blurs the focus. This chapter begins by showing that accidents in the chemical process industry cost lives and dollars. Descriptions of deadly chemical accidents are presented to show the chain of sequences that were involved to suggest how their PSA may be structured. Background on selected hazardous chemical process is presented followed by descriptions of how their PSA have structured. The chapter concludes by applying FTAPSUIT to a pressure vessel rupture analysis.

7.1 Chemical Process Accidents 7.1.1 The Accidents

Nature

of

Process

Accidents follow three steps as illustrated by the following chemical plant accident: A worker, walking across a high walkway in a process plant, stumbles and falls towards the edge, grabs a nearby valve stem, but the valve stem breaks and flammable liquid discharges forming a vapor that is ignited by a truck. The explosion and fire spreads for six days to destroy the plant with a loss of $4,161,(XX). The lesson: minor accidents can lead to large consequences. The three steps are:

Table 7.1-1 Safety Enhancement Action Use: Grounding and Bonding, Inciting, Electrical Explosion-Proof, Guardrails and Guards, Maintenance Procedures, Hot- Work Permits, Human Factors Design, Standard Process Designs, and Awareness of Hazards. Propagation Minimize Hazardous Materials, and Flammable Quantities, Maximize: Use of Non-flammable, Equipment Spacing, and [nstall: Check and Emergency Shutoffs. Termination Have: Firefighting Equipment and Procedures, Relief and Sprinkler Systems.

Step Initiation

Initiation - the event that starts the accident. Propagation - the event or events that maintain or expand the accident. Termination - the event(s) that stop the accident or diminish it in size. Initiation was the worker tripping; propagation was the valve breaking, followed by

245

Analyzing Chemical Process Safety Systems

explosion and fire; termination was the burning of all combustibles. 1982-86 Safety engineering tries to eliminate 1972-76 initiators and replace propagation 1967-71 steps by termination events. Table 0.5 1 1.5 2 Losses in Billion 1997 Dollars 7.1-1 from Crowl and Louvar (1990) presents some ways to achieve this Fig. 7.1-1 Increasing Cost of Process Accidents per goal. While accidents are prevented from M&M, 1997 by eliminating initiators, it is more practical to attack all steps. l i \ ~^

Nature of Process Accidents J&H Marsh and McLendon (M&M, 1997), every five years, reviews and analyzes the 100 largest property damage losses in the hydrocarbon- chemical industries that occurred over the previous 30 years. Most of the losses involved fires or explosions, flood, windstorm, and pressure rupture losses. Figure 7,1-1 shows an increasing trend in the cost of these accidents, including inflation. The five-year period from 1992-1996 had three times more losses than the period 1967-1971. The period 19871991 had the largest total loss and also the largest number of losses (31), which is about five times more loss than the period 1967- 71. The total cost of the 100 losses is $7.52 billion in 1997 dollars, The largest loss was $252,500,000, from a vapor cloud explosion at a gas processing plant at Cactus, Mexico. The average loss was $75,800,000. Figure 7.1-2 Shows the losses

Petrochemical j j [ Refineries - ...,'. 7::T:v:,:::t.:.:":r:. ••.:•'.•;:....::" :"'...,;,::;,; ;;. . i Miscellaneous Terminals - •TTrzT^~rrri'

20

2,5

4 Year Period

i

40 60 80 100 Average Loss in Million 1997 Dollars

120

Fig. 7.1-2 Average Loss by Type of Plant

Vapor Cloud Explosions -j Explosions 1 Fires t Other -u

20 40 60 80 100 Average Loss in Million 1997 Dollars

0

120

Fig. 7.1-3 Average Loss by Loss Mechanism (from M&M, 1997)

Operational Error l=m De$ign Error -£=~ Process Upset Mechanical Failure Unknown Natural Hazard Sabotage/Arson -£

0


100

Fig. 7.1-4 Average Loss by Loss Cause (from M&M, 1997) Reactors

Process towers Marine Vessels ims ienr _nks Unknown Process Drums Miscellaneous Heaters-BoHers

40

Fi

&


7J 5 Avera

8e ^°w by TyPe of Equipment (from M&M, 1997)

'

by type of plant; Refineries, Petrochemical Plants, Gas Processing Plants, Terminals, and Miscellaneous, which includes: an industrial resin coatings plant, a paint manufacturing plant, a synthetic fuels plant, a natural gas transmission compressor station, and a crude oil pipeline pump station. 246

Single losses were most costly at refineries than in any other type of plant at an average loss of $73,700,000. The second most costly accidents occurred at petrochemical plants with an average loss of $80,800,000. Although only 7% of the losses occurred at gas processing plants, the highest average loss was $117,800,000. Figure 7,1-4 ranks fires third, but it is the second most frequent type of loss. The most devastating losses involved delayed ignition of vapor clouds, which account for the highest average toss of $110,900,000. Vapor cloud explosions accounted for the greatest percent of large losses, however, if losses of lesser magnitude were considered, the percent of losses involving fires would exceed that of vapor cloud explosions. The most frequent loss mechanism (43%) was mechanical failure of equipment which was second in terms of average loss at $72,100,000 (Figure 7.1-4). Operational error was the second most frequent cause of loss (21%), but it had the highest average loss ($87,400,000). The type of equipment most frequently involved in accidents was Piping Systems (33%) at an average loss of $76,900,000 (Figure 7.1-5). The second most frequently involved type of equipment was tanks (15%) with an average loss of $61,900,000. While Reactors accounted for on ly 10% of the losses, but had the highest average loss of $151,800,000. This information shows the large costs of accidents in the process industries. The next section shows the deadly effects that process accidents can have and commends us to reducing their frequency and effect through the use of PSA. 7.1.2 Some Deadly and Severe Chemical Accidents

7,1.2.1 Five Hundred and Seventy Six Die in Texas City Disaster3 The port, along with much of Texas City, was ripped apart on April 16, 1947 after a cargo ship, the S.S. Grandcamp, exploded during a shipboard fire. Fueled by 2,300 tons of ammonium nitrate fertilizer (the same potentially explosive material used in the Oklahoma City bombing) the tremendous blast triggered a series of explosions and fires that killed 576 people, injured 4,000 more and damaged every building in Texas City. On April 11, 1947, the Grandcamp arrived at Texas City, loaded with 16 cases of small arms ammunition, 59,000 bales of fisal binder twine, 380 bales of cotton, 9,334 bags of shelled peanuts, some oil field, refrigeration and farm machinery. The Grandcamp docked at Warehouse Pier O, next to Monsanto Chemical Co. plant. Over the next few days, it was loaded with the rest of its cargo. The ammonium nitrate fertilizer was in 100-pound, 6-ply paper bags. (Although Alfred Nobel had included ammonium nitrate in his original formula for TNT, few people - even experts - recognized the potential danger of the granulated, fertilizer-grade variety.) The U.S. Department of Agriculture didn't consider the wax-covered granules hazardous when packed in paper bags or wooden containers, as long as the fertilizer was segregated from other explosives. The Grandcamp was loaded with: 2,300 tons of ammonium nitrate fertilizer, 29,000 bales of sisal twine, 9,334 bags of shelled peanuts, automobiles, trucks, and agricultural machinery, oil, a

From Texas City Disaster website, http://rf.rexl.boise.id.us/v/research.pl/rfrexlboise/ 029277723X/av/880107/key 1 d/qpremiums 247


tobacco, 16 cases of small arms ammunition, and 380 bales of cotton. Shortly after 8 AM, a longshoremen smelled smoke. No one knows what started the fire, but it was speculated that it was caused by a discarded cigarette on the ship in disregard of "No Smoking" signs posted on the wharf. The fire didn't cause much alarm; there were no warnings about the explosive potential of ammonium nitrate - the dockyard workers thought it was inert. The longshoreman, who spotted the smoke, alerted his coworkers who moved several fertilizer bags and found some flames between the cargo and the hull. They tossed a jug of drinking water on the fire, and sprayed it with a fire extinguisher. The flames just got worse. Some of the crew members started hauling boxes of the small arms ammunition out of hold No. 5. The men fighting the fire in the No. 4 hold called for a hose line, but before they could use it, the ship's captain, Charles de Guillebon, intervened. Water would ruin the cargo, he said. The captain instructed his men to close the hatch to the No. 4 hold, cover it with a wet, heavy tarpaulin and activate the ship's steam smothering system in an attempt to suffocate the flames. The steam and decomposing fertilizer, however, combined to create combustible gas. The hatch cover blew off. Thick columns of orange and brown smoke billowed into the air. De Guillebon gave the order to abandon ship. Someone called the Texas City Fire Department; the first firefighters arrived at 8:40 AM; the Grandcamp was out of control. All four engines of the Texas City Fire Department were at the dock, along with several ambulances and 27 of the city's 50 volunteer firefighters. Streams of water from their fire hoses vaporized as soon as they hit the deck of the burning ship. Flames shot out of the hatch. The inside of the ship had turned into a blast furnace. W.H. "Swede"1 Sandberg, the vice-president of the Texas City Terminal Railway, hurriedly called an engineer at a nearby chemical plant and asked whether burning ammonium nitrate was dangerous. Don't worry, came the reply, "It won't explode if it doesn't have a detonator." At 9:12 a.m., the Grandcamp disintegrated in a blast heard 150 miles away. Everyone standing near the ship was obliterated. Most of the spectators and all of the firefighters were killed, many instantly. Some survivors later recalled hearing two explosions. Investigators theorized that the ammonium nitrate in hold No. 4 exploded, propelling the 7,176-ton ship about 20 feet into the air. Heat from the first blast then detonated the rest of the fertilizer in hold No. 2, The blast pushed a 15-foot wave of water out of the harbor. It thrust Longhom II, a 150-foot hydrochloric acid barge, about 500 feet inland and dumped it on railroad tracks. The shock wave from the blast destroyed several dockside warehouses. The large Monsanto plant, only several hundred feet from the Grandcamp, turned into a heap of twisted steel and burning rubble. Flying shrapnel fanned out over the city. Within a mile of the dock, almost every home either collapsed or was so badly damaged it was later declared a total loss. Chunks of debris, some weighing five tons, punctured steel tanks located in chemical tank farms. Streaking overhead like cornets, flaming debris - including bales of sisal twine from the Grandcamp's cargo - torched hundreds of thousands of gallons of oil, gasoline, benzene and propane that flowed from ruptured reservoirs and pipelines. A IVi-ton anchor from the Grandcamp made a 10-foot hole in the ground at the Pan American Refinery Co. after a flight of 1.62 miles. This is an abbreviated description of the damage. Changes resulting from the disaster were: «

An appreciation of the explosive potential of ammonium nitrate. Shipping it from Texas City is forbidden. 248

»

* *

«

*

The city developed an Industrial Mutual Aid System that has been copied all over the world. It incorporates resources from city government, police and fire departments and all of the industries at the port. Emergencies covered in the plan range from simple chemical spills and vapor leaks up to Category Five hurricanes and jetliner crashes. The refineries and the port base decisions on safety - not economics. The city's fire department now has 60 full-time employees, modern fire engines, foam-spraying trucks and other vehicles to combat hazardous materials spills and fires of all sizes, Texas City has a four-tiered warning system for emergencies. Level Four includes activation of the city's warning sirens, the signal for residents to tune into radio and TV broadcasts for additional emergency information. They have had 4 Level Four alerts in 5 years. Sheltering-in-place has become common throughout the country where there is industry like that at Texas City.

7.1.2.2 Chemical Explosion at Kyshtym - Southern Urals, USSR September 29, 1957 an explosion occurred at Kyshtym, a nuclear weapons facility concerned with recovery of plutonium and its waste production. The facility began operation in 1949 using the sodium acetate process. Three large 80,000 gal. waste storage tanks were involved in the accident that held 2E7 Ci of waste in 100 gm/f! concentration with sodium acetate in 60-80 gm/l! concentration. The cooling of one tank failed and the instrumentation was faulty. Water in the solution evaporated, the temperature continued to rise, and at 380° C, a nitrate explosion occurred with about 10 tons of TNT yield to lift the 160 ton concrete shielding cover from the tank, releasing 2 million Curies (Chernobyl released 50 million Curies). The two other tanks were damaged. An evacuation was ordered for the 23,000 km2 area about the facility involving 10,000 people. Before the accident, the operators fled from the heat emanating from the tank, which may be the reason that no fatalities were reported. 7.1.2.3 Twenty Eight Die at Flixborough5 On June 1, 1974, a vapor cloud explosion destroyed Bellows the 70,000 tons per year, Flixborough Nyprocyclohexane oxidation plant killing 28 people. Other plants on the site were seriously damaged or destroyed and the site was destroyed. ' ^ Temporary Pipe Section The plant was a stage in the production of nylon. It Fig 7 l 6 Tem manufactured a mixture of cyclohexanone and cyclohexanol - ~' P°rary RePair at , ,, , , .. . ,. . Fhxboroueh T, . „ (known as KA, for the ketone/alcohol mixture) by oxidizing cyclohexane, a hydrocarbon similar to gasoline, in a series of reactors. When cyclohexane at 155° C and 7.9 atm is depressurized to atmospheric pressure, it vaporizes. The liquid reaction mass, flows b

Adapted from the Flixborough web site: http://www.dyadem.com/papers/flixboro.htm and Growl (1990). 249


by gravity, through the series of reactors. Reactor 5 developed a leak, was removed and replaced by a temporary jumper pipe (Figure 7.1-6). Each reactor normally contained about 20 tons of cyclohexane. No professional mechanical engineer was on the site at the time. The workers designed and installed the pipe by judgment from experience and got the plant on line in a few days. However, they did not allow sufficiently for the stress on a 20 inch pipe at 150 psi pressure, or the weakening of the metal from operation at 150° C (302 °F). It was designed on a chalkboard in the workshop and installed with jerry-rigged scaffolding Several months before the accident, reactor 5 in the series was found to be leaking. Inspection showed a vertical crack in its stainless steel. It was removed for repairs, but it was decided to continue operation by connecting reactor 4 directly to reactor 6 in the series. The loss of the reactor reduced the yield but production continued with unreacted cyclohexane being separated and recycled at a later stage. The feed pipes connecting the reactors were 28 inches in diameter. Since only 20-inch pipe stock was available at the plant, the connections between reactors 4 and 6 used bellows sections. The bypass pipe section ruptured from inadequate support and over-flexing. When the bypass ruptured, an estimated 30 tons of cyclohexane volatilized into a large vapor cloud that ignited from an unknown source about 45 seconds after the release. The resulting explosion leveled the entire plant facility, including the administrative offices. Twenty-eight people died and 36 others were injured. Eighteen of these fatalities occurred in the main control room when the ceiling collapsed. Loss of life would have been greater if the accident had occurred during normal working hours. Damage extended to 1,821 nearby houses and 167 shops and factories. Fifty-three members of the public were reported injured. The fire in the plant burned for over ten days. This accident could have been prevented or mitigated by safety procedures: I) the jumper pipe was not designed for the operating conditions, 2) unsuitable material was used, 3) it was installed without a safety review or competent supervision, and 4) the plant site contained excessively large inventories of dangerous compounds. On site were: 330,000 gallons of cyclohexane, 66,000 gallons of naphtha, 11,000 gallons of toluene, 26,400 gallons of benzene, and 450 gallons of gasoline that contributed to the fires after the initial blast. 7.1.2.4 Dioxin Released at Seveso, Italy0 On July 10, 1976 a major chemical accident occurred outside of Seveso, near Milan, at a plant operated by Icmesa S.p.A., a company belonging to the Roche Group. A reaction vessel containing the intermediate trichlorophenol overheated. The resulting excessive pressure ruptured the disk of a safety valve. This released a mixture of chemicals, including highly toxic dioxin, which settled on large areas of the communes of Seveso, Meda, Cesano Maderno and Desio. In the days and weeks that followed, a number of people reported inflammation of the skin and chloracne.

c

Adapted from the Seveso website: http://www.roche.com/roche/about/esevesgl.htm and Crowl(1990), 250

Chickens and rabbits died, and many people had to be evacuated from their homes. Over the next weeks, months and years, Roche helped alleviate the consequences of the accident through: 1) compensation for the damage suffered by private citizens and public bodies, 2) medical examinations of the affected population, and 3) paying compensation for any damage to health. The injuries were few and transient, hence, the compensations were modest in comparison with those for property damage. The affected population is still undergoing long-term observation, including regular check-ups. In cleaning up the site, dioxin-contaminated waste from the reaction vessel were packed in forty-one barrels that went astray in May 1983. They were eventually found in 1985 in the northern French town of Anguilcourt-le-Sart at an abattoir. Their contents were burned in a Ciha high-temperature incinerator. The plant's product was hexachlorophene, a bactericide, with trichlorophenol produced as an intermediate. During normal operation, a very small amount of TCDD (2,3,7,3 tetrachlorodibzoparadioxin) is produced in the reactor as an undesirable side product. TCDD is perhaps the most potent toxin known to man. Studies have shown TCDD to be fatal in doses as small as 1E-9 times the body weight. It insolubility in water makes decontamination very difficult. Nonlethal doses of TCDD result in chloracne, an acne-like disease that can persist for several years. On July 10, 1976, the trichlorophenol reactor went out of control, resulting in higher than normal operating temperature and increased production of TCDD. An estimated 2 kg of TCDD was released through a relief system in a white cloud over Seveso. Subsequently, heavy rain deposited the TCDD contaminating about ten square miles of soil. Local authorities, due to poor communications, did not start civilian evacuation until several days later; by then, over 250 cases of chloracne were reported. Over 600 people were evacuated and an additional 2,000 were given blood tests. The most severely contaminated area immediately adjacent to the plant was fenced, the condition it remains in today. A similar release occurred in Duphar, India in 1963, after which the plant was disassembled brick by brick, encased in concrete and dumped into the ocean. Less than 200 grams of TCDD were released at Duphar, and the contamination was confined to the plant. Fifty men did the clean up; four eventually died from the exposure. These accidents would have been prevented by: 1) adequate process safety design, 2) proper procedures to prevent the initiation, 3) hazard evaluation procedures to identify and correct hazards before accident occurrence, and 4) containment systems to prevent release into the atmosphere.

7.1.2.5 Twenty-Five Hundred Die at Bhopal, India* The Accident At about 12:40 A.M. December 3, 1984, the accident occurred that took 2,500 lives at the Union Carbide (India) Ltd. (UCIL) operated pesticide plant. The first indication of process upset was when the control-room operator (CRO) noted that the temperature in a supposedly refrigerated tank storing methyl isocyanate gas (MIC), had risen to 77° F. The pressure, normally 2 to 25 psi was 55 psi. d

Adapted from Shrivastava (1987) and Crowl (1990). 251


While running to the storage tank area, the CRO heard a loud rumbling sound and saw a plume of gas rising from the stack. The supervisor, CRO, and several other operators, actuated safety devices including the storage tank refrigerator and the scrubber. When these failed, they ran. Nearby residents, feeling a burning sensation in eyes and throat, also ran. The district collector and the superintendent of police, were awakened by telephones and rushed to the police control room to coordinate emergency relief efforts. The police and the army tried to evacuate affected neighborhoods, but were too slow, and gave improper directions, resulting in 200,000 residents fleeing into the night. Morning showed the devastation with thousands of injured victims streaming into the city's hospitals. Doctors and other medical personnel struggling with the chaos knew neither the cause of the disaster nor how to treat the victims. They treated the immediate symptoms by water washing eyes, applying eye drops, giving aspirin, inhalers, muscle relaxants, and stomach remedies. The official death toll was 2,700, more than 300,000 exposures to the poison, 2,000 dead animals and 7,000 injured animals. Aggravating the accident was industrial growth over the last thirty years, without the supporting infrastructure, resulting in dense slum housing near the plant. Narrow streets and the absence of Fig. 7.1-7 Common Headers to the MIC Storage Tanks at Bhopal transportation made evacuation ineffective. MIC is a highly toxic substance used for making carbaryl, the active agent in the pesticide Sevin 12. It is highly unstable and needs to be kept at low temperatures. UCIL manufactured MIC in batches and stored it in three large underground tanks (Figure 7.1-7) until it was needed for processing. Two of the MIC tanks had met specifications, the third had not. A schematic layout of the storage tanks and the various pipes and valves involved in the accident. A stainless-steel header branched to deliver MIC to each of the storage tanks as shown in Figure 7.1-8). MIC was transferred out of the storage tanks by pressurizing the tank with high-purity nitrogen. Once out of the tank, MIC passed through a safety valve to a common relief header that led to the production reactor unit. Another common line took rejected MIC back to the storage tanks for reprocessing or sent contaminated MIC to the vent-gas scrubber. Excess nitrogen was regulated

252

by a blow-down ,—& To Process-Vent Header From High-Purity Nitrogen Header valve. Though they served different purposes, the relief-valve pipe and the process pipe were connected by a jumper that had been installed about a year before the accident to simplify maintenance. Each Refrigentttoa Unit storage tank had separate temperature and Mixing Educlor "^ Sump pressure gauges loFig. 7.1-8 MIC Storage Tank at Bhopal cated locally and in the distant control room. Each tank had a high- temperature alarm, a level indicator, and high- and low-level alarms. The safety valve through which MIC escaped was redundant with an unmonitored graphite rupture disk. Checking it required manual inspection of a pressure indicator located between the disk and the safety valve. A safety feature of the plant was the vent-gas scrubber that neutralized toxic exhausts from the MIC plant and storage system. Off-gas scrubbed with caustic soda was discharged at a height of 100 feet and routed to a flare. The tower flare burned normally vented gases from the MIC section and other units in the plant to detoxify the gases before venting them into the atmosphere. However, the flare was not designed to handle large quantities of MIC vapors. A few weeks before the accident the scrubber was placed in standby. The vapor pressure of MIC was kept low by a thirty-ton freon refrigeration system that chilled the salt water coolant for the MIC storage tank. However, the refrigeration system was shut down June 1984, and its coolant was drained for use in another part of the plant, thus making it impossible to switch on the refrigeration system during an emergency. An additional safety feature was a water-spray to scrub escaping gases, or deluge over-heated equipment, or fires. The last batch of MIC, before the accident, was produced in the interval October 7-22, 1984. At the end of the campaign the E610 storage tank contained about 42 tons of MIC, and the E611 storage tank contained about 20 tons. After which, MIC production was shut down, and parts of the plant were dismantled for maintenance. The flare tower was shut down to replace a piece of corroded pipe. Forty-three days before the accident, the nitrogen pressure in E610 dropped from 17 (about normal) to 3.5 psig. Lacking pressure in E610, any MIC needed in the manufacturing process was drawn from E611. But four days before the accident, tank E611 also lost pressure because of a bad valve. An attempt to pressurize E610 failed, so the pressure system for E611 was repaired. On the night before and early morning of the accident, a series of human and technical errors caused the water for flushing pipes to pass through several open valves and flow into the MIC tank. The water and MIC reacted to produce a hot and highly pressurized gas, foam, and liquid, that

253


discharged through the plant's stack into the atmosphere. Normally, water and MIC reacting in small quantities in the plant's pipes create a plastic called trimer which is periodically removed by water flushing. But this reaction of water and MIC was so volatile that a blind flange was used to block the discharge pipes. In the evening before the accident, the second-shift production superintendent ordered the MIC plant supervisor to flush out several pipes that led from the phosgene system through the MIC storage tanks to the scrubber. Although MIC unit operators were in charge of the flushing operation, insertion of a blind flange was the responsibility of the maintenance department. The position of second-shift maintenance supervisor had been eliminated several days earlier, hence, the blind flange was not inserted, nevertheless the flushing operation began at 9:30 P.M. Downstream from the flushing, several clogged bleeder lines caused water to backup in the pipes. Many valves leaked, including the one for isolating the lines being flushed. This resulted in water passing through that valve into the relief pipe. Noting the absence of flow from the bleeder lines, the operator shut off the flow, but was ordered to turn it back on by the MIC plant supervisor. Water flowed from the relief pipe (20 ft elevation) to tank E610. It first flowed through the jumper to the process pipe to the normally closed blow-down valve which was open (possibly inadvertently left open or failed to seat in the attempt to pressurize the tank). About 119 gallons of water flowed through this open blow-down valve, through another, normally open, isolation valve to enter tank E610, where it reacted with MIC. At 11 P.M., after a shift change, the new control-room operator, noticed that the pressure in tank E610 was 10 psi, well within the operating range of 2-25 psi. One-half hour later, a field operator saw MIC near the scrubber; MIC and dirty water were discharging from a branch of the relief pipe downstream of the safety valve. They also found that a process-safety valve had been removed, and the open end of the pipe was not blocked for flushing. The control room was informed. By 12:15 A.M., the pressure in tank E610 had risen to 30 psi and rising. Within 15 minutes it pinned at 55 psi. A hissing sound came from the popped safety valve; local temperature and pressure gauges showed values beyond their maximurns of 77° F and 55 psi; loud rumblings and heat radiation came from the tank. An attempt was made to activate the scrubber from its standby mode, but caustic soda was not circulating. A cloud of gas discharged from the stack. The plant superintendent suspended operations and sounded the toxic-gas alarm to warn the community. A few minutes later the alarm was turned off with only the in-plant siren warning workers in the plant. Operators turned on the firewater sprayers to douse the stack, the tank mound, and the relief pipe to the scrubber. The water spray did not reach the gas, which were being emitted at a height of 30 meters. The supervisors tried to turn on the refrigeration system to cool the tanks, but failed because the coolant had been removed. The 400° F, 180 psi discharge continued for two hours. Because of proximity to the slums, thousands of people were exposed to this lethal mixture. Twenty-four hundred people died, thousands more were injured; 2,000 animals were killed; the environmental damage was considerable. The hospitals, dispensaries and morgues were overloaded and could not accommodate the flow of injured victims.

254

Causes of the Accident * » * * « * * *

» * * * » 9

* * * * 9

* « * * * * * «

Insufficient staff quality and training Lack of safety culture Job insecurity Ongoing labor-management conflicts Carelessness in operations Lack compliance with rules Multiple responsibilities High turnover rate Elimination of the position of maintenance supervisor on the second and third shifts (this was a direct cause of the failure to install the blind flange) Lack of personnel for backup, inspections, control, and checking Lack of emergency planning and training Turning off the alarm that warned the public Failure to investigate causes of equipment inoperability and permitting the storage of hazardous material e.g. the failure of tank E610 pressurization Failure to make corrections that were found in a safety audit conducted two years before the accident Failure to maintain pressurization of MIC tanks resulted in contaminations that catalyzed the exothermic reaction. Poor design that stored MIC in large tanks The scrubber and offgas equipment were not designed to mitigate accidents Operation with the flare tower inoperable Lack of electronic emergency communications within the plant, and with neighbors Inability of the water spray to reach the discharge gases Inoperability of the refrigeration system Failure of a relief valve Lack of fixed water-spray protection in several areas of the plant Maximum allowable scrubber pressure of 15 psi while the rupture disk allowing gas to come into the scrubber was rated 40 psi. A spare tank was not empty to accept MIC transfer Tank E610 was filled to 75 to 80% of capacity; but 50% was recommended Failure to maintain a safe exclusion zone about the plant Flushing of pipes without investigating the blockage

T.1.2.6 Two Die in Ammonium Dichromate Explosion6 A January 17, 1986 explosion at a Diamond Shamrock Chemical plant near Ashtabula, Ohio, killed two employees, critically injured another, and caused lesser injuries to at least a dozen other workers. The blast involved 2,000 Ib of ammonium dichromate in the unit for its production at the plant.

Adapted from C&EN, January 27, 1986. 255


Ammonium dichromate is an intermediate in the manufacture of many important chromium chemicals, including pigments and magnetic recording materials. It is made by reacting chromium(VI) oxide in aqueous solution with ammonia. One of the final steps in the process involves drying the bright red-orange crystals in a rotary vacuum dryer. It was in that unit that the explosion took place. Ammonium dichromate decomposes on heating to yield nitrogen gas, water vapor, and chromium(in) oxide that was seen as a green cloud over the accident site. The wind carried the cloud over Lake Erie to dissipated. Diamond Shamrock notes that chromiuni(ni) oxide can cause skin irritation but is otherwise nontoxic, however OSHA sets the threshold limiting value for chromium(III) oxide in air at 0.5 mg per cubic meter. 7.1.2.7 Three Thousand Evacuate Hydrofluoric Acid Leak at Texas City1 October 31, 1987 a hydrofluoric acid leak occurred at a Marathon Petroleum Co. refinery leading to the evacuation of 3,000 people over a 52-block area and hundreds of injuries. Hydrofluoric acid is used in many oil refineries as an alkylation catalyst. On the day of the accident, refinery workers were using a crane to lift a 40-ton convection section from a hydrofluoric acid heater. At about 5:20 PM, the crane failed and the piece fell severing pipes that were connected to a vessel containing the hot acid. Hydrogen fluoride gas spewed from the broken pipes to form a cloud that spread over the city. Cooling of the vessel began immediately; by about 6:30 PM, acid was being transferred from the vessel to transport trucks and railway tankcars. In three days, the vessel was empty and the facility was safe. No plant employees were injured, many people were afflicted with inflamed eyes and lungs as a result of the fumes; 140 patients were admitted for observation and treatment for exposure to the gas. About 800 people were seen, treated, and released. Marathon set up a claims office; by the next day 600 people filed; from Texas City and nearby towns; filing went on for several days. Hydrofluoric acid is highly corrosive to skin and mucous membranes. Even in fairly low concentrations, it causes painful skin burns and severe damage to eyes and the respiratory system. Exposure at higher levels results in destruction of tissues and death. No one in Texas City was exposed to more than trace concentrations of hydrofluoric acid. The acid vessel had a capacity of about 850 barrels of which a small fraction was released. Other circumstances mitigating the accident were: the hydrogen fluoride gas was hot and rose rapidly; it was dissipated quickly by a brisk, dry wind; only several small pipes were broken, so the leak was fairly easily controlled.

f

Adapted from C&EN, November 9, 1987. 256

7,1.2.8 Three Die in Explosion at Hoechst Ceianese Plant9 November 14, 1987, three people were killed when two explosions and a fire caused extensive damage to the Hoechst Celanese acetic acid and acetic anhydride plant located near Pampa, TX. Also on the Pampa site was a specialty resins plant operated by Interez, a unit of RTZ Corp, which was interrupted because it depends on power supplied from the main Hoechst Celanese operation. The cause of the explosion, which also left four people seriously injured and 31 others with minor injuries, is unknown. A Hoechst Celanese spokesman says that the first blast occurred near a gas-fired boiler and the second blast at a nearby reactor in which butane is reacted with steam to produce acetic acid. The 35-year-old plant employs 600 persons, 150 as contract maintenance and construction workers, but the blasts on Saturday only involved a weekend crew of 60. A plant team working with the Pampa fire department brought the fire under control. The Chemical Manufacturers Association's Community Awareness & Emergency Response Program (CARE), developed after the Bhopal disaster was credited with effectiveness of their efforts in putting out the fire. Hoechst Celanese officials said it was too early to decide whether to rebuild the butane reactor, install a newer methanol-to-acetic acid process, or start up a standby acetic acid facility at Bay City, TX, to replace the idled 350-million-lb per year acetic acid plant. 7.1.2.9 Two Workers Die and Solid Rocket Fuel Supply Destroyed11 May 4, 1988, explosions leveled a Pacific Engineering & Production Co. (PEPCO) plant, at Henderson, NV, one of only two U.S. plants producing 20 million lb/ year (maximum of 40 million Ib/year - see Table Table 7.1-2 Ammonium Perchlorate 7.1-2) ammonium perchlorate for solid rocket fuel. It was the Use in Rockets (million Ib/year) principal supplier for the space shuttle and sole supplier for the User 1988 1989 1990 Titan rocket and several military missiles. Army 14.0 11.7 9.3 The explosion killed two workers, injured 350 local Navy 5.4 3.7 6.5 residents, destroyed property up to 20 miles away, and Air Force 11.0 11.5 16.1 damaged 50% of Henderson's 17,000 residential and NASA 19.8 22.1 8.5 commercial buildings. The two largest blasts registered 3.0 Commercial 3.5 3.7 5.2 and 3.5 on the Richter scale hundreds of miles away in 2.6 European 1.8 5.3 Other 2.0 1.0 2.0 California, cars were crumpled, doors blown off their hinges, Total 38.8 60.1 67.8 and windows shattered for miles around. Uninsured losses were more than $20 million, plus $3 million more in insurance deductibles. Just as serious, were the psychological and emotional impact of the explosions, on schoolchildren and adults. g

Adapted from C&EN, November 23, 1987.

h

Adapted from C&NE, June 13 and August 8, 1988. 257


The fire department blamed the accident on: welders cutting in hazardous areas without a fire watch, highly combustible structural components (fiber-glass-resin), high-density storage of highly flammable and detonable material, spilled ammonium perchlorate about the plant, and high wind conditions, The disaster brought an awareness for the potential hazards of the Kerr-McGee plant, just 0.7 mile from the center of town. Such was expressed at a hearing held by the Subcommittee on Investigations & Oversight of the House Committee on Science, Space & Technology, The U.S. faced a crisis in its space and missile programs over the three years following the accident because of shortages of the solid fuel oxidizer ammonium perchlorate. A recovery strategy was formed by an interagency group, including members from DOD and NASA in liaison with the Departments of Commerce and Transportation. The first step is to restart Kerr-McGee and raise its capacity to 40 rnillion/lb a year. Then, with federal aid, Kerr-McGee and PEPCO will build new plants with 20 million Ib and 30 million Ib annual capacities, respectively, but not in Henderson, Before reopening, the plant adopted safety measures such as: • • • »

Dispersal of the barrels of ammonium perchlorate stored outdoors about the site, An additional blender to expedite shipments and reduce stored inventory, Greater emphasis on safety, and Involvement with the public and their concerns.

7.1.2.9 One Dies in BASF Plant Explosion8 A reaction vessel explosion at BASF's resins plant in Cincinnati (July 19, 1990) killed one and injured 71. The BASF facility manufactures acrylic, alkyd, epoxy, and phenol-formaldehyde resins used as can and paper-cup liner coatings. The explosion occurred when a flammable solvent used to clean a reaction vessel vented into the plant and ignited. The cleaning solvent that was not properly vented to a condenser and separator, blew a pressure seal, and filled the 80-year-old building with a white vapor cloud. 7,1.2.11 Eight Die at Nitroparaffin Plant in Sterlington, LA1 The explosion and fire (May 1,1990) caused eight deaths (including a vice-president and site manager), 120 injuries, extensive damage to buildings in the area, and evacuation of an entire small town. The cause of the explosion, at the Angus Chemicals Plant, was the blowout of a compressor line on the nitroparaffin unit.

1

Adapted from C&EN, July 30, 1990.

j

Adapted from C&EN, May 6 and May 13, 1991. 258

Across Louisiana State Highway 2, a hospital, local school, and nearby residences were damaged by the blast. On the site, the administration building was damaged but other processing units had little damage. IMC Fertilizer's two ammonia production units were not damaged. Emergency response and investigative teams moved in rapidly despite previous flooding and continued bad weather. Efforts initially concentrated on shutting down propane supply lines to the unit, stopping a leaking nitric acid tank perforated by the blast, and putting out fires that were limited lo the plant site and were under control by early the next morning. Within a few hours of the blast, all Sterlington was evacuated for fear of leaking toxic chemicals. Residents were allowed to return on May 3 after no leaks were found. Damage to the surrounding area was extensive. Many residences had windows blown out or were damaged by large pieces of piping and metal thrown by the explosion.

7.1.2.12 One Dies in Union Carbide Ethylene Oxide Plant Explosion" An explosion and fire (March 13, 1991) occurred at an ethylene oxide unit at Union Carbide Chemicals & Plastics Co.'s Seadrift plant in Port Lavaca, TX, 125 miles southwest of Houston. The blast killed one, injured 19, and idled the facility, that also produces ethylene, ethylene glycol, glycol ether ethanolamines, and polyethylene. Twenty-five residents were evacuated for several hours as a safety precaution. The plant lost all electrical power, for a few days, because its cogeneration unit was damaged. The Seadrift plant, with 1,600 workers, is capable of making 820 million Ib per year of ethylene oxide which is one-third of Carbide's worldwide production of antifreeze, polyester fibers, and surfactants; Seadrift produces two thirds of Carbide's worldwide production of polyethylene.

7.1.2.13 Six Die in Charleston Explosion' An explosion and fire at an Albright & Wilson Americas phosphorus chemicals plant in Charleston, SC (June 17,1991) killed six and injured 33. The damaged unit lost part of its walls and roof. Eight other units on the 200 employee site, sustained minor or no damage, but were shutdown for a few days. At the time of the accident, plant workers were mixing chemicals in the No, 2 reactor in the special products unit when an explosion and fire occurred. Five of the people killed were contract employees not directly involved with the reactor, but were installing insulation nearby. Ironically, the reactor was used to produce Antiblaze 19, a flame retardant used in textiles and polyurethane foam. Antiblaze 19 is a cyclic phosphorate ester produced from a mixture of trimethyl phosphite, dimethyl methylphosphonate (DMMP), and trimethyl phosphate (TMOP). The final product is not considered flammable, but trimethyl phosphite is moisture sensitive and flammable, with a flash point of about 27° C. k

Adapted from C&EN, March 18, 1991.

1

Adapted from C&EN, June 24, 1991.

259


7.1.2.13 Six Die in Benzoic Acid Explosion in Rotterdam"1 December 13,1991, a benzole acid tank exploded causing six deaths and three injuries at the Dutch chemical firm: DSM's chemical complex in Rotterdam Harbor. Shipping traffic was halted for an hour in the world's busiest port while the fire was controlled. A platform was being constructed from one storage tank to another, without the workers knowing that mixture of benzoic acid and air in the open storage tank could explode. DSM is the largest European producer of benzoic acid which is used in a range of applications from a plasticizer to food preservative. DSM's capacity here is 440 million Ib per year.

7.1.2.15 Four Die at Fertilizer Plant Explosion" An early morning explosion, Dec. 13, 1994, killed four employees and injured 18 at Terra Industries' Port Neal, Iowa, nitrogen fertilizer plant, 16 miles south of Sioux City. The blast leveled half the facility and forced evacuation of more than 2,500 people from nearby towns with an ammonia cloud released from a ruptured storage tank. Road and air traffic were diverted. Some were injured by falling debris and others by the impact of the explosion. Many suffered from ammonia inhalation. The plant employed 119 people in three shifts, but only 30 were there when the explosion occurred. Terra's plant produced about 12% of the U.S. nitrogen-based liquid solution fertilizer. About one half of the plant was totally destroyed, the other half of the plant was damaged. The explosion was heard 50 to 60 miles away and shook Sioux City. The explosion occurred in the ammonium nitrate production area. Shrapnel from the blast ripped open a 15,000 ton anhydrous ammonia storage tank, releasing an ammonia plume that could be smelled 30 miles away. A two-mph wind kept the ammonia from dissipating quickly. Metal fragments punctured a nitric acid tank, spilling up to 100 tons of 56% nitric acid. The ammonia tank, initially about one-third full, stopped leaking when the fluid level dropped below the puncture. Off-plant damage included blown windows and doors torn off their hinges. There was also structural damage to a nearby power plant. Emergency crews responded from Iowa, Nebraska, and South Dakota. A State Emergency Operations Center was activated. EPA, OSHA, the Coast Guard and the Department of Transportation were among the many federal, state, local, and private agencies participating the response.

111

Adapted from C&EN, December 23, 1991.

n

Adapted from C&EN December 19, 1994. 260

Chemical Processes

7.1.2.16 Four Die at New Jersey Chemical Plant Explosion A slow response to a smoldering mix of chemicals at the Napp Technologies plant in Lodi, NJ is blamed for an April 21,1995 explosion and fire that killed four workers and injured dozens of others. The blast destroyed more than 70% of the plant, which made pharmaceutical and cosmetic intermediate products, and employed 110 workers. The explosion wrecked several stores housed in the Napp building, damaged nearby buildings, and forced evacuation of 400 residents for about 13 hours. Chemicals leaked into a nearby river, killing hundreds of fish. The explosion occurred 12 hours after a gold precipitating process went awry. Problems began in the evening of Thursday, April 20, with clogging of a line that supplied benzaldehyde to a vacuum tumble dryer. A mix of 1,000 Ib of aluminum powder and 8,000 Ib of sodium hydrosulfite was already in the unit. Workers, trying to clear the blockage inadvertently introduced water into the vat. The water set off a smoldering reaction, but little was done to stop the reaction until the 6 AM shift change. The plant was evacuated at 6:30 AM; A chemist recommended nitrogen to smolder the reaction, but it was too late. At 8 AM, heat from the sodium hydrosulfite-aluminum water reaction reached the flashpoint of aluminum and it exploded and caused a fire. 7.1.2.17 More than Thirty Die at Chinese Dye Factory Explosion0 An explosion at a dye factory at Tianjin, near Beijing, killed more than 30 people and injured at least 60 workers and residents. The blast occurred June 26, 1996 at the China Petrochemical Factory (Dabua Huagongchang). The explosion was strong enough to shatter windows as far as 2 miles away and to create a crater about 10 feet deep and 90 feet in diameter. All buildings in an area of several thousand square yards were flattened; a steel beam from the factory's roof was thrown about 160 feet and a mixing furnace flew about 500 feet. The incident started when sodium in a sulfurization process ignited. The blast occurred shortly after workers attempted to put out the fire with water.

7.2 Chemical Processes 7.2.1 The Topography of Chemical Processes

Chemical Reactors and Nuclear Reactors Nuclear power reactors cause the transmutation of chemicals (uranium and plutonium) to fission products using neutrons as the catalyst to produce heat. Fossil furnaces use the chemical reaction of carbon and oxygen to produce CO2 and other wastes to produce heat. There is only one reaction and one purpose for nuclear power reactors; there is one reaction but many purposes for fossil-burning furnaces; there are myriad chemical processes and purposes. All chemical processes involve bringing atoms of selected types in close proximity for the

0

Adapted from C&EN, July 8, 1996. 261


atomic forces to react and produce other chemicals. In addition to producing chemicals, heat is produced which may or may not be detrimental. Temperature and pressure are thermodynamic parameters that must be controlled to get the reaction started and to control the reaction. Thus, chemical processes consist of the ingredients listed in Table 7,2-1. Accidents result when the reaction rate becomes uncontrollable and the confinement fails. Taxonomy of the Chemical Process Industry13

Table 7.2-1 Chemical Process Steps

The chemical process industry is vast and • Get materials to be reacted varied. The value of chemicals and chemical products • Bring the chemicals together in confinement vessels called reactors in 1993 was $0.5 trillion for the U.S,q involving 67,000 • Supply or remove heat chemical engineers, 98,000 chemists. There were 5.5 • Control temperature and pressure non-fatal occupational injuries per 100 employees in • Use catalysts, light, and/or electricity 1995 involving chemical and allied products, and 4.8 per 100 workers in petroleum and coal products. There • Remove and process wastes. were 101 fatalities due to exposure to caustic, noxious or allergenic substances and 208 deaths from fires and explosions in 1995. The following is a list by major heading of processes in the Chemical Industry. While accidents can occur in any activity, the scope of the chemical process industry is so wide that processes are selected for description based on judged hazard. These are identified by the number of the section in which they are described. Process not identified by a three digit number are excluded on the basis of low perceived accident potential. 7.2.2 7.2.3 7.2.4

Inorganic chemicals Fertilizers Organic chemicals: Soaps and detergents Dyes Pharmaceuticals

7.2.5 7.2.6 7.2.7 7.2.8

Explosives Rubber Plastics and resins Man-made fibers Paints and Varnishes Papermaking Petrochemical Processing

7.2.2 Inorganic Chemicals Chlorine and Products The Leblanc process for converting table salt (NaCl) to sodium carbonate (NaCO,) for soap

p

The following description of the chemical process industry is adapted from Britannica

(1990). q

Information from the 1997 U.S. Statistical Abstracts website, http://www.census.gov. prod/www/abs/cc97stab.html.

262

Chemical Processes

and glass production was invented in 1793. In the first step, sodium chloride was treated with sulfuric acid to produce sodium sulfate and hydrogen chloride. The sodium sulfate was heated with limestone and coal to produce black ash which contained sodium carbonate mixed with calcium sulfide and unreacted coal. The sodium carbonate (soda ash) was removed by filtration, and crystallized. The hydrogen chloride gas damaged vegetation so it was converted to elemental chlorine, absorbed in lime to form bleaching powder. Thus, a liability was converted to an advantage. Because calcium sulfide contained in the black ash had a highly unpleasant odor, methods were developed to remove the odor by recovering the sulfur, therein providing at least part of the raw material for the suifuric acid required in the first part of the process. Thus, the Leblanc process demonstrated, at the very beginning, the typical ability of the chemical industry to develop new processes and new products, and often in so doing to turn a liability into an asset. The Leblanc process was replaced by the ammonia soda (Solvay - 1860) process, in which sodium chloride brine is treated with ammonia and carbon dioxide to produce sodium bicarbonate and ammonium chloride. Sodium carbonate is obtained from the bicarbonate by heating. Ammonium chloride treated with lime gives calcium chloride and ammonia. The chlorine in the original salt becomes calcium chloride that is used for melting snow and ice. The ammonia is reused in the process (99.9% recovery). The development of electrical power made possible the electrochemical industry. Electrolysis of sodium chloride produces chlorine and either sodium hydroxide (from NaCl in solution) or metallic sodium (from NaCl fused). Sodium hydroxide has applications similar to sodium carbonate. The advantage of the electrolytic process is the production of chlorine which has many uses such as production of polyvinyl chloride. PVC, for plumbing, is produced in the largest quantity of any plastic. Sulfur and Products Sulfuric acid is, by far, the most widely manufactured chemical. Burning sulfur, in air produces sulfur dioxide, which, when combined with water, gives sulfurous acid. Combining the dioxide with oxygen forms the trioxide which, when combined with water forms sulfuric acid. When this process take place in a chamber, it is called the "chamber" process. The contact process which replaced the chamber process reacts the products using a platinum or a vanadium catalyst. About half of the world's production of sulfuric acid goes to producing superphosphate and related fertilizers. Other uses are many, such as the manufacture of high-octane gasoline, of titanium dioxide (white pigment - a filler for some plastics and paper), explosives, rayon, uranium processing, and the pickling of steel. Sulfur was mined from volcanic deposits in Sicily, but is mined under by liquefaction. It is also obtained from the ore iron, pyrite, by burning to produce sulfur dioxide, and from some natural gases (sour gas), that contain hydrogen sulfide. It also is obtained from roasting zinc or copper sulfides to release sulfur dioxide. The sulfur present in low percentages in fossil fuels is a notorious source of air pollution in most industrial counties. Removal of sulfur from crude oil adds to the sulfur supply and reduces pollution. It is more difficult to remove sulfur directly from coal.

263


Ammonium sulfate fertilizer is made by reacting ammonia with sulfuric acid. In many parts of the world, calcium sulfate is in mineral form convertible to ammonium sulfate by combining it with ammonia and water - a virtually limitless source of sulfur. Carbon disulfide is made by reacting carbon from natural gas, and sulfur from hydrogen sulfide, or sulfur dioxide. Carbon disulfide is used to make rayon and regenerated cellulose film,

7.2.3 Fertilizer Production Potassium

Air, 1-ossA'FiiH

Two of the previously mentioned accidents salts I Synthesis, Gas, and the Oklahoma City bombing showed the explosive potential of nitrogen fertilizer so this is a good place to start. Fertilizers represent one of the largest i Specialized Elements needed for markets for chemicals. agriculture are nitrogen, phosphorus, and potassium; Fertilizers hxplosives calcium, magnesium, and sulfur are secondary Fig. 7.2-J Fertilizers and Uses nutrients; copper, zinc or molybdenum are needed in trace quantities, Nitrogen makes up 78 % of the atmosphere, hence, it is readily available. Ammonia is produced by fixing of atmospheric nitrogen with hydrogen. Mineral sources of phosphorus and potassium are converted to a suitable form for fertilizer. These three elements have other use than fertilizer; they are used and interact with other facets of the chemical industry, making a highly complex picture, A schematic of the interactions is presented in Figure 7.2-1. Potassium The seventh element in order of abundance in the Earth's crust is potassium - about the same as sodium with similar properties. While sodium is readily available from the ocean, potassium is found and extracted from many mineral formations. About 90 percent of the potassium that is extracted goes to the production of fertilizers. Other purposes for it are ceramics and fire extinguishers for which potassium bicarbonate is better than sodium bicarbonate. Phosphorus By far the largest source of phosphorus is phosphate rock, with some use of phosphatic iron ore, from which phosphorus is obtained as a by-product from the slag. Phosphate rock consists of the insoluble tricalcium phosphate and other materials. For use as a fertilizer, phosphate must be converted to the water soluble form, phosphoric acid (H3PO4) which has three hydrogen atoms, all of which are replaceable by a metal. Tricalcium phosphate, is converted to soluble monocalcium phosphate and to superphosphate. A fertilizer factory, typically, a large installation, characterized by large silos; produces year round, but peaks with the demands of the growing season. Phosphorus has many uses other than for fertilizer. The weight of the superphosphate can be reduced by replacing sulfuric acid with phosphoric acid (obtained by sulfuric acid acting on phosphate rock followed by product separation, or by the

264

Chemical Processes

electric furnace process). This process results in triple superphosphate, in which all the calcium originally in the phosphate rock appears as calcium monophosphate. The efficacy of the fertilizer is the high percentage of phosphoric oxide, which may be 45% in the triple variety, hence, twice as effective as fertilizer. Instead of using sulfuric or phosphoric acid, nitric acid can be used to treat the phosphate rock to produce calcium nitrate fertilizer. Instead of neutralizing phosphoric acid with calcium which is useless, ammonia can be used to give ammonium phosphate, hence, two fertilizing elements. A use other than fertilizer is phosphoric acid and the various phosphates derived from it for soft drinks. Disodium phosphate is used in: cheese processing, baking powder, flame proofing, treatment of boiler water in steam plants, and detergents. Elemental white phosphorus is used for rodent poisoning and for military smoke screens. Red phosphorus, is used in matches, Ferrophosphorus is an ingredient in high-strength low-alloy steel. Organic compounds of phosphorus are additives in gasoline, lubricating oil, plasticizers for plastics, insecticides, and related to nerve gas. Nitrogen In 1914, while abundant in the atmosphere, natural supplies of nitrogen in manure and in deposits of sodium nitrate were insufficient to meet the demand of war The solution was the Haber process for producing ammonia (NH3) by heating hydrogen and nitrogen gas at high pressure. Hydrogen is obtained by decomposing water (H2O) using heat or electricity. Burning coke and water produces steam, carbon monoxide, and hydrogen (water gas). Water gas reacts with steam and a catalyst to yield more hydrogen, and carbon dioxide which is removed by water dissolution. The mixture of carbon monoxide and hydrogen is the synthesis gas for methanol as shown in Figure 7.2-1 as the source of ammonia and methanol. The hydrogen for ammonia is obtained from the water-gas shift reaction. Originally the process used coke from coal or lignite (brown coal), but these has been replaced by petroleum products and natural gas. The carbon dioxide removed in synthesis gas preparation can be reacted with ammonia, to form urea CO(NH2)2. This is an excellent fertilizer, highly concentrated in nitrogen (46.6%) and also useful as an additive in animal feed to provide the nitrogen for formation of meat protein. Urea is also an important source of resins and plastics by reacting it with formaldehyde from methanol. Ammonia is used as a fertilizer by injecting it beneath the soil surface, or by mixing it with irrigation water. Granular ammonium nitrate is applied directly. Other uses for ammonia are making sodium carbonate using the ammonia soda process. It also is used for making rayon, as a refrigerant in commercial refrigerators and as a convenient portable source of hydrogen. Liquefied ammonia is used as a high density source of hydrogen for metallurgical processes in which ammonia is decomposed by heat to release the hydrogen and nitrogen. Nitric Acid The most important use of ammonia is in the production of nitric acid (HNO3). Ammonia bums in oxygen, releasing hydrogen to form water and free nitrogen. With the catalysts platinum and rhodium, ammonia is oxidized and reacted with water to form nitric acid. Nitric acid treated

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with ammonia gives ammonium nitrate for use as a fertilizer. It is also a constituent of explosives. Three fundamental explosive materials are obtained by nitrating (treating with nitric acid, often in mixture with sulfuric acid): cellulose nitrate from wood, nitroglycerin from glycerol, and TNT from toluene. Another explosive ingredient is ammonium picrate (2,4,6-trinitrophenol) from picric acid. Detonating agents, or such priming caps are lead azide [Pb(N3)2], silver azide (AgN3), and mercury fulminate [Hg(ONC)2]. These are not nitrates or nitro compounds, but they contain nitrogen from the use of nitric acid in their manufacture. Related to explosives are rocket propellants for missiles or spacecraft launch vehicles. Rocket propellants consist of an oxidant and a reductant. The oxidant is not necessarily a derivative of nitric acid, but may be liquid oxygen, ozone (O3), liquid fluorine, or chlorine trifluoride. Other uses for nitric acid, not related to explosives or propellants, are in the production of cellulose nitrate for use in coatings. Without a pigment it forms a clear varnish used in furniture finishing. Pigmented, it forms brilliant shiny coatings called lacquers. Nitrating benzene yields nitrobenzene which can be reduced to aminobenzene, better known as aniline. Aniline also can be made by reacting ammonia with chlorobenzene. Similar treatment applied to naphthalene (C,0 H8) results in naphthylamine. Both aniline and naphthylamine are the parents of a large number of dyes, but today synthetic dyes are usually petrochemical in origin. Aniline, naphthylamine, and the other dye intermediates lead to pharmaceuticals, photographic chemicals, and chemicals for rubber processing. Synthesis of ammonia must be done free of oxygen compounds that will poisons the catalyst, hence, all traces of carbon dioxide and carbon monoxide must be removed. A typical plant has large compressors and other equipment for the preparation and purification of the synthesis gas on the requisite scale. High pressure increases the yield at the expense of compression. Low temperature increases the yield, but as the temperature is lowered the reaction slows. The temperature that is chosen is about 500° C (930° F) to optimize results. Each time a fraction of the synthesis gas is converted to ammonia, therefore, after each pass the ammonia is removed and the remaining gas is recycled. Atmospheric nitrogen contains about 1 % argon, a totally inert gas, which must be removed from time to time so that it does not build up in the system indefinitely. The nitric acid factory has equipment for producing ammonium nitrate in the grain size convenient for fertilizer. Growing plants do not receive all of their nitrogen from synthetic fertilizer. Some is supplied naturally by nitrogen-fixing plants, notably beans, in a symbiotic relationship with bacteria,

7.2.4 Halogens and Their Compounds Chlorine The first large-scale use of chlorine was for bleaching paper and cotton textiles; it also is widely used as a germicide for public water supplies. Presently it is used principally in production of the chemical compounds: sulfur chloride, thionyl chloride, phosgene, aluminum chloride, iron(IH) chloride, titanium(IV) chloride, tin(IV) chloride, and potassium chlorate. Organic chemicals made directly from chlorine include derivatives of methane: methyl chloride, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene ortho- and paradichlorobenzenes; ethyl chloride, and ethylene chloride. The oldest process for chlorine production used hydrochloric acid reacting with manganese 266

Chemical Processes.

dioxide. This was superseded by the 1868 Deacon process that reacted atmospheric oxygen with the hydrochloric acid, from the Leblanc soda ash process. The chlor-alkali process uses simultaneous production of chlorine and sodium hydroxide by electrolytic decomposition of salt (sodium chloride) using brine is the electrolyte, and graphite rods as the anodes. An alternative process uses iron or mercury as the cathodes. Passage of a direct current through brine causes chemical reactions where the electrodes contact the electrolyte. At the graphite anode chloride ions present in the dissolved salt are oxidized to elemental chlorine which goes to a vent. At the iron cathode, hydrogen gas is removed, while the hydroxide ions remain in the solution. The net result is that chloride ions and water are consumed and chlorine gas, hydrogen gas, and hydroxide ions are produced. Complete conversion of chloride to hydroxide is not practical, but as brine is continuously introduced at the top of the cell, a solution containing nearly equal amounts of salt and caustic soda is withdrawn at the bottom. Purification of this yields solid sodium hydroxide and a small amount of salt. Successful production of chorine and caustic soda in these cells requires that the two products be separated, because they would react with one another if mixed. Chlorine is separated from the caustic by a diaphragm between the electrodes (diaphragm cell). The other main variant of the chlor-alkali process employs a mercury cell. The cathode is a shallow layer of mercury flowing across the bottom of the vessel. Graphite anodes extend down into the brine electrolyte. Direct current passes between the graphite rods and the mercury surface. At the anodes, chloride ions are converted to chlorine gas as in the diaphragm cell. The reaction at the mercury cathode is different from the reaction at an iron cathode. Positively charged sodium ions in the brine migrate to the mercury surface where the voltage is high enough to reduce them to sodium metal, but water is not reduced because of the mercury potential. The metallic sodium formed at the cathode dissolves in the mercury, and the amalgam flows out of the cell into another vessel, where it contacts water to forms sodium hydroxide and hydrogen. A mercury cell produces the same results as a diaphragm cell: sodium chloride and water are changed into sodium hydroxide, chlorine, and hydrogen. The mercury cell generates sodium hydroxide free of sodium chloride. This higher purity is needed for certain products such as the manufacture of rayon. Fluorine The fluorine industry is intimately related to aluminum production. Aluminum oxide, (A12O3) is electrolyzed to metallic aluminum with a flux of sodium fuoroaluminate (Na3AlF6), called cryolite - a rare mineral found in commercial quantities only in Greenland with other uses: glass, enamels, and as a filler for resin-bonded grinding wheels. Synthetic cryolite solved the supply problem, but synthetic cryolite requires fluorine which is actually more abundant in the Earth's crust than chlorine, but dispersed in small concentrations in rocks. Until the 1960s, fluorspar (CaF2) a mineral long known and used as a flux in various metallurgical operations was the source. A source is phosphate rock that contains fluorine is 3% quantity. Organic fluorine as a separate industry that began in the late 1920s with the discovery by Midgle of fluorocarbons for use as refrigerants. Ammonia was unsuitable because of the hazard and unpleasant smell from minute leaks. Sulfur dioxide had similar problems. The best refrigerant was

267


Freon 12 (CCljF^ which is now banned by the ozone protection treaty. Also used is Dichlorodifluoromethane, Freon 22 (CHC1F2), and chloro-difluoromethane. Several analogous compounds containing carbon, fluorine, chlorine, and sometimes hydrogen are available, Another application is uranium hexafluoride for enriching uranium in the fissile isotope uranium-235 by diffusion. Fluorine is known for being difficult to handle because of its intense chemical reactivity. The solution required the development and use of fluorine-resistant materials so that fluorine manufacture is now routine. Other uses developed: as a component in some rocket propellants, for the preparation of the extremely reactive interhalogen compounds such as chlorine trifiuoride (C1F3), used for cutting steel, and for the preparation of sulfur hexafluoride, an extremely stable gas that has been employed as an insulator in electrical applications. Other uses are teflon, a fluorocarbon resin such as poly-tetrafluoroethylene for coating frying pans to prevent food from sticking. There are several other fluorocarbon and fluorinated hydrocarbon resins; some have highly specialized applications in the aerospace industry. Fluorinated compounds are also used in textile treatments; some are soil-release agents that make fabric easy to wash. The salt: sodium fluoroacetate is an extremely powerful rodenticide. Sodium bifluoride is used to remove iron stains without weakening fabric. A minor but important use of fluorine in some countries is the fluoridation of drinking water for dental health. Bromine The properties of bromine are different from those of fluorine and chorine, and it is far less abundant. It was discovered in the early 19th century, as a salt (bromide) in the bitterns remaining after evaporating seawater and extracting sodium chloride for use as medicine. It was found in the production of potassium salts and from salt lakes. It gained industrial importance as an emulsion of silver bromide particles in gelatin for making photographic film. Tetraethyllead was used to prevent knocking in car engines using ethylene dibromide, often in mixture with ethylene dichloride. The supply from brines from the Great Lakes and from the Dead Sea, at about 5 parts bromine per thousand, was insufficient for the demand. An alternative is the use of seawater at 70 parts per million in which a small amount of sulfuric acid is added for acidification. Then chlorine, which releases bromine, is absorbed by sodium carbonate and released by sulfuric acid. Besides the use of ethylene dibromide in gasoline as a lead scavenger, it is used as a fumigant, as a solvent for certain gums, and in further syntheses as is methyl bromide which also is used as a fumigant and fire extinguisher. Iodine On a smaller scale, the largest producer of iodine is Japan where it is extracted from seaweed containing more than 0.05 parts per million. The most important industrial iodine compound is silver iodide used with silver bromide in photography. Iodine is important in medicine for treating thyroid problems by adding it to table salt. It is used directly as a disinfectant, and a component of dyes. Crystalline silver iodide is used for cloud seeding.

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Chemical Processes

7.2.5 Organic Chemicals Originally the chemical industry was inorganic; in the 1960s organic chemicals (means they , , . contain carbon) came into . , ^ prominence with the compounds: r benzene, phenol, ethylene, and vinyl chloride. The organic chemicals: benzene, phenol, toluene, and the xylenes compose the aromatic group. t

1

ii»nz,n Plastics carbide production is suitable for a i Nitrogen i rioeri i Acetaldehyde country with hydroelectric power but cy i Conversion tu Acrylonitrile Gasoline Acetic Acid Fertilizers! Chloroprei Stvrene Comonents lacks petroleum reserves. Calcium and Acetic Anhydride Weedi i Butadiene Killers Rubbe' 1 ^ Acryinmtrile Neoprene carbide generates acetylene when (nil; innej I Rubber Meljmine ~~ * . . Nitnle Rubber Plastics acted upon by water. The quantity produced may be small such as using Fig. 7.2-3 Unsaturated Hydrocarbons from Petroleum the bright flame of acetylene for lighting, or oxyacetylene welding, or large such as chemical manufacturing. Acetylene and ethylene compete as a chemical raw material. Ethylene is generally more economical, resulting in declining use of acetylene as a raw material. Calcium carbide, a raw material for acetylene has other uses. Treated with nitrogen, it gives calcium cyanamide, valuable as a fertilizer and weed killer, and a raw material for the production of melamine, used in making some modern plastics.

Propylene Propylene is produced in less volume than acetylene or ethylene. It is a raw material for 270

Chemical Processes

detergents; derivatives used in antiknock gasoline additives. It can be polymerized to a product with uses similar to those of polyethylene. As a fibre, it is useful for carpets and rope. Elastomers Butadiene (Figure 7.2-3) is used for plastics and elastomers. Elastomers were originally synthetic substitutes for natural rubber. Research led to a copolymer of 75 parts butadiene and 25 parts of styrene (SBR) - styrene-butadiene rubber. It is often blended with other rubbers to get the best properties. Figure 7.2-3 shows that acrylonitrile can be copolymerized with butadiene (roughly 1/3 acryionitrile, 2/3 butadiene) to form nitrile rubber (NBR). This synthetic has different properties and is used for rubber hose, tank lining, conveyor belts, gaskets and wire insulation. Acrylonitrile and styrene, together with butadiene, form a terpolymer, called ABS, which is useful for high-impact-strength plastics. Acrylonitrile contains nitrogen, and therefore is different chemically from natural rubber, which contains only carbon and hydrogen. Natural rubber's molecule is a repeating unit of five carbon atoms. By starting with the unsaturated hydrocarbon isoprene (C5H8), a synthetic natural rubber polymer can be made with the same spatial arrangement of atoms and properties as natural rubber. Another hydrocarbon elastomer starts with isobutylene (C4H8) and gives butyl, a rubber that is resistant to oxygen and impermeable to gases; it is used as cable insulation and as a coating for fabrics. Figure 7.2-3 shows acetylene as the raw material for chloroprene (C4H3C1), which converts to neoprene. Rubber-like products that contain sulfur are known as thiokols. Related tough plastic materials containing carbon, sulfur, and oxygen are the sulfones,

Film materials Most of the above can be made into plastic films - primarily used for wrapping. Film properties vary widely from permeable for food to impermeable to preserve dryness. Paper, treated or untreated, has been used for many years as a covering film, but has low strength when wet and is difficult to make transparent. In the 1920s, the transparency of cellophane revolutionized wrap, It is regenerated cellulose, like viscose rayon, except it is extruded in sheet instead of fiber, unfortunately it is sensitive to water and humidity. Many other polymers compete with cellophane such as polyethylene which is extruded as a tough film or in greater thickness as a nonbreakable bottles. Vinyl products used in films are polystyrene, polyesters, and nylon. A chemical derivative from nature rubber, chlorinated rubber, gives films of extraordinary stretch ability. Closely related to films are paints. Previously linseed oil, thinned with turpentine, formed the film into which were imbedded pigments. Turpentine, from pine trees, is still used, but competes with a petroleum distillate (less smelly). Water-based latex paints are a water emulsion of an organic paint that is thinned with water.

Carbon Slack Carbon black dominates as black pigment. It is a petrochemical made from natural gas or petroleum residues by incomplete combustion - cooking to split the hydrocarbon into hydrogen and carbon. Its primary use is in compounding rubber for making tires of which an average passenger

271


car tire contains four pounds of carbon black. Carbon black is used in printing ink, but is difficult to remove for recycling. A carbon black is as an additive to phonograph records; a special form from acetylene, is used in electrochemical dry cells. An important form of alcohols is methanol (Figure 7.2.1) synthesized from carbon monoxide and hydrogen. Methanol is called wood alcohol because it was obtained by distilling wood. About half of its production goes to making formaldehyde (CH2O), a very reactive, widely used chemical. Methanol is used to produce various plastics and derivatives such as methyl chloride, a solvent for inks and dyes, and in the purification of steroidal and hormonal medicine. It is used to form important groups of plastics: the urea-formaldehyde resins; it is used as a fungicide and preservative, in paper and textile treatments, and in the synthesis of other products. Ethanol and its Products Methanol (CH3OH) is the simplest form of alcohol; the next is ethanol (CH3CH2OH), with two carbon atoms. It is the intoxicating drink. For industrial use it is fermented from cheap material such as molasses, or made from ethylene by causing it to combine with water using a catalyst (sulfuric acid or phosphoric acid). Oxidation to acetaldehyde (CH3CHO) is a major industrial use of ethanol. It could be in Figure 7.2-3 between ethylene and the block containing acetaldehyde and related chemicals. Ethanol is used to produce ethyl chloride (for tetraethyl lead), making various plastics, and in the further syntheses. Acetaldehyde may be made from ethanol in the same plant. Alcohol, for human consumption, is highly taxed, but this tax is avoided by denaturing with methanol to make it poisonous. There are two possible structures (isomers) of three carbon atom alcohol. One is n-propyl alcohol (or 1-propanol), the other is isopropyl alcohol (or 2-propanol). The former, not manufactured in large quantities is used in printing inks. The latter is manufactured in millions of tons to make propylene by a process similar to that used to convert ethylene to ethanol. The manufacture of 2-propanol by this process initiated the petrochemical industry in the 1920s. A principal use of 2-propanol is to make acetone, a solvent, and as a starting material in making other organic compounds. Smaller amounts of 2-propanol are convened to other chemicals or used as a solvent, rubbing alcohol, or denaturing agent for ethyl alcohol. Higher alcohols have more than three carbon atoms. Examples are the dihydric alcohol, ethylene glycol used for: antifreeze, brake fluids and as derivatives in: resins, paints, explosives, and polyester fibers. Reactions with propylene make propylene glycol, a moistening agent in foods and tobacco,

7,2.6 Explosives Chemical explosives detonate, or deflagrate. Detonating explosives (e.g., TNT or dynamite) rapidly decompose to produce high pressure and a shock front (travels faster than the velocity of sound). Deflagrating explosives (e.g., black and smokeless powders) bum fast, produce lower pressures and no shock front. In large quantities and with confinement, deflagrating explosives may detonate. Detonating explosives are primary or secondary. Primary explosives detonate by flame, 272

Chemical Processes

spark, impact, or other heat sources of sufficient magnitude. Secondary explosives require a detonator and, in some cases, a supplementary booster. Some explosives are primary or secondary depending on conditions. Black Powder

Black powder, a mixture of potassium nitrate, sulfur, and carbon, may have been invented in tOth century China for fireworks. There is written record they used it in bamboo tubes to propel stone projectiles. There is evidence that Arabs invented it around 1300 A. D. using a gun made of bamboo with iron bands to fire an arrow. Roger Bacon wrote its recipe in 1242, as a Latin anagram, but may have read it in Arabic. The modern process for black powder begins with charcoal and sulfur in a hollow drum with heavy steel balls. This ball mill pulverizes the contents as the drum rotates through the tumbling of the steel balls. The potassium nitrate is crushed separately using heavy steel rollers. A mixture of several hundred pounds of potassium nitrate, charcoal, and sulfur goes onto a cooking pan where it is continuously turned over by plows. Next, it is ground and mixed by two rotating iron wheels, each weighing about 10 tons. The process takes several hours with water being added to keep the mixture moist. The product is put through wooden rolls to break up the larger lumps and formed into cakes under about 4,000 psi pressure. Coarse-toothed rolls crack the cakes into manageable pieces and the mixture is rolled to the desired size. Glazing (a graphite coating to make it flow better) tumbles the grains for several hours in large wooden cylinders to round the corners while forced air circulation adjusts the moisture content. After glazing it is graded by the size of the grains. Black powder is relatively insensitive to shock and must be ignited by flame or heat. In the early days, glowing tinder or heated rods ignited a powder train leading to the main charge to give the firer time to reach a safe place. Cannons used a touchhole in the breech filled with fine powder for ignition by slow-burning punk. Black powder is still used in guns that cannot withstand the pressures of smokeless powder. The use of black powder in underground coal mines is no longer allowed in most counties. The low production makes black powder more expensive than dynamite. However, there is no substitute for black powder in certain military applications and nothing is equal to it for the manufacture of safety fuse. Black powder was used in constructing the Mont Cenis (eight-mile) railway tunnel through the Alps connecting France and Italy (1857-1871). Nitroglycerin

Nitroglycerin was discovered by Ascanio Sobrero, in 1846. Its danger made it a laboratory curiosity until Alfred Nobel improved it along with other inventions such as the blasting cap using mercury fulminate. The first large scale nitroglycerin factory in the U.S. was built by George Mobray to complete the Hoosac Tunnel (4 miles) at North Adams, Massachusetts in 1867. This plant, before closing, produced about 1-million pounds of nitroglycerin without accidents in either manufacture or shipment. An early use of nitroglycerin in the U.S. was blasting oil wells to increase their flow of oil. Another use was the construction of the Sutro silver mine in Nevada (1864-1874), Frozen pure nitroglycerin (52° F) is relatively insensitive and easily kept frozen by packing 273


it in ice. In cold climates, this presented a problem in thawing that was best overcome with different explosives, Dynamite In 1867, Nobel invented dynamite (Greek meaning "power") based on his discovery that kieselguhr earth absorbs nitroglycerin thereby making a safer explosive. The next step was replacement of the inert-earth absorber with combustible material (wood pulp) using a sodium nitrate oxidizer. Blasting action was controlled by adjusting the ratio of nitroglycerine to absorber. Nobel invented gelatinous dynamite in 1875 by accident. He investigated the effect of nitroglycerine on the collodion (nitrocellulose in a mixture of ether and alcohol) that he used to treat a cut finger and found that it produced a tough plastic material with adjustable viscosity and high water resistance. The high freezing point of nitroglycerin affects dynamite. Frozen dynamite is very insensitive, undependable and difficult to punch for blasting cap. Accidents occurred in thawing. In 1907, low-freezing dynamite was developed by adding 25% of the liquid isomer TNT (discussed later) to the nitroglycerin, or nitrated sugar in glycerin. In 1911, diglycerin (a glycerin polymer) was nitrated to produce tetranitrodiglycerin with a lower freezing point than nitroglycerine. The ultimate solution was nitrating ethylene glycol (a common antifreeze) to produce ethylene glycol dinitrate with properties practically identical to those of nitroglycerin, but low freezing. Dynamite made of it and nitroglycerin was stored in the open at Point Barrow, Alaska, for four years without freezing, Ammonium Nitrate An important advance in dynamite was the substitution of ammonium nitrate for part of the nitroglycerin to produce a safer and less expensive explosive. Nobel made this new dynamite successful by devising gelatins that contained from 20 to 60 percent ammonium nitrate. Ammonium nitrate was too hygroscopic, hence, work began to develop a nongelatinous form. , The solution, found in 1885, was coating ammonium nitrate with a little paraffin to produce a series of ammonia dynamites. Major underground coal-mining countries regulate explosives by specifying those that are permitted. Practically all allowable explosives have ammonium nitrate as the major ingredient, because of its low explosion temperature. Nearly all contain a cooling agent such as table salt or ammonium chloride to prevent the heat of explosion in a mine from igniting methane or coal dust. With inexpensive synthetic ammonia, and natural gas, explosives shifted from ammonium nitrate for nitroglycerin in the forms: 1) low-density ammonia dynamites and 2) semigelatins. Control of the blast and heat of explosion minimized nitroglycerin and a maximized ammonium nitrate, with dilution by low-density ingredients such as cane fibers to reduce the cost per stick. The semigelatins with a high nitroglycerin content are partially gelatinized with nitrocellulose. This gelatinization provides water resistance and plasticity that is desirable in loading holes prior to blasting. A moderate amount of water resistance in the ammonia dynamites, without gelatinization of nitroglycerin, can be achieved with water-repellent calcium stearate, or ingredients that form a water gel on the surface of the dynamite to slow the penetration of water. Ammonium nitrate-fuel oil mixtures (ANFO) and ammonium nitrate-base water gels marked

274

the biggest change in the explosives industry since dynamite. They now constitute more than 70% of the high explosives use in the United States because both ANFO and water gels are delivered in bulk by special trucks and loaded directly into boreholes. In 1955 it was discovered that mixtures of ammonium nitrate and fine coal dust have satisfactory blasting capabilities in large (9-inch) holes used in open-pit coal mines to remove the rock and soil covering the coal. Polyethylene bags containing this material deform to fit the hole and provide moderate water resistance. ANFO is used in open-pit iron and copper mines and for construction such as road building. The mixture is air blown into 2-inch holes or less in many underground mines. ANFO uses prilled rather than crystallized ammonium nitrate. Prills are free-flowing pellets developed for fertilizer as a coarse product with little setting tendency that can be spread easily and smoothly. A small amount of selguhr earth is added to improve the flow properties. Prills are made by tower dropping molten ammonium nitrate droplets. While falling, they dry as a slightly porous solid that absorbs oil to form a more sensitive product than in crystalline form. ANFO is a mixture of 94% prills and 6% No. 2 fuel oil that imparts water resistance which is enhanced by polyethylene bags. Water gels, introduced in 1958, were mixtures of ammonium nitrate, TNT, water, and gelatinizing agents (guar gum and a cross-linking agent such as borax). Sometimes aluminum and other metals were used and better gelatinizers have been developed. In addition nonexplosive sensitizers were developed to dilute the TNT. Water gels have the advantages of: high yield, high degree of water resistance, plasticity, ease of handling and loading, and good safety characteristics, Nitrocellulose Schoenbein invented guncotton in 1845 by dipping cotton in a nitric and sulfuric acids in hope for a better propellant for military weapons, but it reacted too fast. A successful propellant was made in 1860, by nitrating wood in nitric acid, dissolving the acid, and impregnated the pieces with barium and potassium nitrates to supply oxygen for burning the incompletely nitrated wood. This powder worked in shotguns but was too fast for rifles. In 1884, smokeless powder was made by dissolved nitrocellulose in ether and alcohol until forming a gelatinous mass that was rolled into sheets and cut into flakes. The product, after the solvent evaporated, was satisfactory for all types of guns. In 1887, Nobel invented "Ballistite" composed of 40% low nitrogen nitrocellulose and 60% nitrogiycerin. Cut into flakes, it was a good propellant. The British ignored his patent and developed a similar product called "cordite." DuPont in the U.S. developed about 1909, a smokeless powder from cotton of relatively low nitrogen that was quite soluble in ether alcohol. A small amount of diphenylamine was used as a stabilizer. After forming the grains and removing the liquid, a coating of graphite was added to make the smokeless powder that was used in the U.S. Other double-base types contain about 25% nitrogiycerin. Cotton lint for nitration has been replaced by purified wood cellulose. TNT Trinitrotoluene TNT is the most useful military high explosive, although it was known for many years in the

275


dye industry, it was not used as an explosive until 1904. The wide spread between its melting point and decomposition temperature gives it the ability to be safely melted and cast either alone or with other explosives. Its shortcomings are its extreme insensitive in the cast form, and the difficulty of casting without air holes. Its insensitivity is overcome by filling a I-inch hole running the length of the explosive charge with tanitrophenylmethvinitramine (tetrvl); porosity is overcome by using a mixture of 40% trinitroxyiene (TNX) and 60% TNT. This mixture not only casts well but can be detonated with a smaller tetryl booster. TNX was replaced by PETN and RDX in World War II. Picric Acid and Ammonium Picrate Ammonium picrate (Explosive D) has exceptional value as a charge for armor-piercing projectiles. Loaded in a shell with a suitably insensitive primer, it can be fired through 12-inches armor plate and detonate on the far side. Early in World War I it was found that mixtures of molten TNT and ammonium nitrate were almost as effective for shell loadings as pure TNT. The mixtures most commonly used were 80-20 and 50-50 AN and TNT, known as amatol. Their advantage is stretching TNT use and reducing cost. Several explosives used in World War H were: RDX, PETN, and. ethyienediaminedinitrate (EDNA). All were cast with about 50% TNT and used where the highest shattering power was needed. For example, cast 60-40 RDX-TNT, called cyclotoJ develops a detonation pressure of about 4-million psi. Mixtures of PETN and TNT have almost as much shattering effect. Compositions C-l to 4 are a series of plastic demolition explosives with great shattering power containing about 80% RDX combined with a mixture of various oils, waxes, and plasticizers. They differ in temperature ranges of usefulness.

7.2.7 Plastics and Resins Plastics, in the modern meaning, are synthetic materials capable of being molded. The Greek word "plastikos" means to form. Natural products, while plastic, are usually excluded. Resins may be natural or synthetic. The distinction between plastics and resins is arbitrary - many synthetic materials are both. Historically, the term resin was applied to synthetic substitutes for the natural product; plastic was applied to compositions involving molding in their fabrication. Customarily, the fiber industry is considered to be distinct from the plastics industry, although it uses the same raw materials - polyamides (nylon), cellulose, and cellulose acetate. Plastics, when heated, soften without melting, to attain a shape that is retained on cooling. They are composed of polymers, with giant molecules having immensely long chains of repeating units of chemically-bonded short molecules called monomers. The bonding forces are: a) the relatively weak London, Van der Waals, or dispersion forces, or b) the strong polar forces, hydrogen bonds or dipole-dipole interactions that result in higher softening temperature. Long polymers are usually tangled and considerable force is required for separation. When heated, the chains separate sufficiently to slide over one another to allow deformation. Plastics are fabricated by molding, i.e., by melting plastic granules and pouring into a mold, extruding, rolling to form sheets, vacuum to form sheets to a mold or blowing from tubes into bottles at moderate temperatures (300 to 480° F). The results are tough, light, and transparent to take coloring. The polymers are either thermoplastic or thermosets which form a network of molecules

276

Chemical Processes

that does not soften on reheating (e.g., phenol-formaldehyde). The first plastic was celluloid, made of nitrocellulose softened by vegetable oils and camphor. It was used for car windshields and for movie film. The first completely synthetic plastic was bakelite (1910) produced from phenol and formaldehyde for use in the electrical industry. Meanwhile, cellulose acetates were intensively studied to produce triacetate, a waterproof varnish to the fabric on World War I airplane wings. Triacetate also was made in powdered form for later melting and molding. With manufacturing development of methylene chloride, triacetate film came into use as a photographic base in 1935. Transparent acetate film was developed, and used for packaging. Vinyl chloride (1835) formed by reacting acetylene with hydrochloric acid, was polymerized as polyvinyl chloride (PVC) in 1912. The theory of polymerization by Staudinger in the 1920s led to the advances that followed. The acrylate were polymerized as polymethylmethacrylate to come into production in 1927. Polystyrene was developed similarly and concurrently. Polyethylene came into production in 1939 for use in radar and now is ubiquitous.

Polymerization The molecular chains of plastics are formed by condensation or addition polymerization, A condensation polymer forms by stepwise reacting molecules with each other and eliminating small molecules such as water. Addition polymer forms chains by the linking without eliminating small molecules. The most important concept in condensation polymers is "functionality," i.e., the number of reactive groups in each molecule participating in the chain buildup. Each molecule must have at least two reactive groups, of which hydroxyl (-OH), acidic endings (-COOH), and amine endings (-NH) are the simplest. Hydroxyl is characteristic of alcohol endings that combine with an acid ending to give an ester which can polymerize to polyester. Examples are polyethylene terephthalate (ethylene glycol - hydroxyl ending and terephthalic acid - two acidic groups) and polycarbonate resins. Alcohols are a class of oxygen-containing chemical compounds with a structure analogous to ethyl alcohol (C2H5OH). Amines are compounds derived from ammonia by replacement of hydrogen by one or more hydrocarbon radicals (molecular groups that act as a unit). Esters are compounds formed by reacting an acid with alcohol or phenol and eliminating water. Bulk addition polymerization of pure monomers is mainly confined to styrene and methyl methacrylate. The process is highly exothermic and heat must be removed to maintain chain length with intensive stirring of the viscous, partially polymerized mixture before passage down an increasing temperature tower. Alternatively, polymerization may be completed in containers that are small enough to avoid an excessive temperature. Methyl methacrylate is partially polymerized before being formed into clear acrylic sheet by molding between sheets of plate glass. Suspension polymerization produces beads of plastic for styrene, methyl methacrylate, vinyl chloride, and vinyl acetate production. The monomer, in which the catalyst must be soluble, is maintained in droplet form suspended in water by agitation in the presence of a stabilizer such as gelatin; each droplet of monomer undergoes bulk polymerization. In emulsion polymerization, the monomer is dispersed in water by means of a surfactant to form tiny particles held in suspension (micelles). The monomer enters the hydrocarbon part of the micelles for polymerization by a 277


water-soluble catalyst. X-rays or ultraviolet radiation may initiate polymerization for the manufacture of thermoplastics such as polyethylene and polyvinyl chloride. Thermosetting Resins Resins not softened by heating are the phenolics: furan resins, aminoplastics, alkyds, allyls, epoxy resins, polyurethanes, some polyesters, and silicones. Phenolics or phenol-aldehydes include the important commercial phenolic resin; bakelite based on phenol and formaldehyde. A one-step process produces resol resin from more than one molecule of formaldehyde per phenol molecule. A two-step process uses an excess of phenol to produce novoiacs - resins that have no reactive methylol groups and must be mixed with an aldehyde to undergo further reaction. Resol resins thermoset on heating and are used for adhesives. Novolacs require a further source of formaldehyde in the form of hexamethylenetetramine to produce molding powders. Phenolic moldings are resistant to heat, chemicals, and moisture with good electrical and heat insulation qualities. Complex phenols from, e.g., cashew-nut shell liquid, are used in making brake linings. Furan resins such as furfural is a five-member ring molecule consisting of four carbon and one oxygen atom. Carrying the aldehyde group, -CHO, it reacts like formaldehyde with phenols in the presence of an acid catalyst to give a rigid polymer with high chemical resistance for industrial coatings. It is used in semi-liquid form having low viscosity and high penetrating power for application to porous forms such as foundry sand cores. Aminoplastics, such as urea resins, are made by condensing in aqueous solution of formaldehyde and urea in the presence of ammonia as an alkaline catalyst. The result is a colorless syrupy solution to which cellulose filler is added to make a molding powder. When heated, the powder melts in a mold and cools to a water-white solid that is strengthened by the filler to make cups and tumblers. Very large quantities of urea-formaldehyde resin are used in kitchens and bathrooms. Melamine behaves similarly to urea, but it is more moisture resistant, harder, and stronger for use in plates and food containers. Melamine moldings are glossy and harder than any other plastic. Solutions of the thermoplastic forms of urea-formaldehyde resins are widely used as bonding agents for plywood and wood-fiber products. Alkyds

Alkyds are polyesters formed of phthalic acid (two acid groups) and glycerol (three hydroxyl groups). The solid resins mold fast under low pressure, cure quickly to produce material with good insulating properties, strength, and dimensional stability over a wide range of voltage, frequency, temperature, and humidity conditions for use as vacuum-tube bases, automotive ignition parts, switchgear and housings for portable tools. Polyesters of Unsaturated Alcohols The resins known as DAP and DA1P, are cross linked allyl esters of phthalic and isophthalic acid, respectively. They are notable for rigidity and excellent electrical properties at temperatures up to 450° F. Allyiic resin-impregnated glass cloth is used in aircraft and missile parts. Other

278

ChemiciiI Processes

applications use the good storage life, and absence of gas evolution during polymerization. The optically clear resin: aHyl diglycol carbonate is used for making cast objects that are more heat and abrasion resistant than other cast resins. Epoxy Resins Epoxy resins have outstanding mechanical and electrical properties, dimensional stability, resistance to heat and chemicals, and adhesion to other materials. They are used for casting, potting, encapsulation, protective coatings, and adhesives. Epoxy glues separate the resin from the curing agent to be mixed just prior to use. Polyurethanes Polyurethanes are formed by reacting diisocyanates and polyols (multihydroxy compounds) to form some of the most versatile of rigid to elastic plastics. A major use is for foams with good flexibility and high rigidity. Thermoplastic polyurethanes can be extruded as sheet of extreme toughness. Polyesters of Unsaturated Acids Certain esters can be polymerized to an infusible resin for use in glass-fiber-reinforced plastics. Unsaturated maleic acid anhydride is polymerized to a relatively short polymer chain by condensation with a dihydric alcohol such as propylene glycol. The chain length is determined by the relative quantities of the two ingredients. The resulting syrup of condensation polymer is diluted with a monomer, such as styrene, or an initiator for addition polymerization. This mixture is quite stable at room temperature. Frequently, a silicone compound is added to promote adhesion to glass fibers, and wax to protect the surface from oxygen inhibition of polymerization. Glass-fibers are impregnated with the syrup and polymerized by raising the temperature. Alternatively, the polymerization is done at room temperature by addition of a polymerization accelerator to the syrup immediately before impregnation. After a controlled induction period exothermic polymerization takes place to give a glass-fiber-reinforced cross-linked polymer. Silicones Silicon, unlike carbon, does not form double bonds or long chains. However, it forms long chains with oxygen such as in siloxanes in which hydrocarbon groups are attached to the silicon producing material for a wide range of oils, greases, and rubbers. By replacing certain atoms in the chain, silicon resins can be used for high- and low-pressure lamination with fibers to produce electrical material having high dielectric strength, and low dissipation over a wide temperature and humidity range. Silicones do not distort in temperatures up to 752° F.

Thermoplastic Resins Resins that soften on heating include: cellulose derivatives, addition polymers, and condensation polymers. Cellulose is a naturally recurring chain carrying three hydrox groups, which can be esterified by acids. Cellulose nitrate (gun cotton) is formed by treating cellulose with a mixture of strong sulfuric and nitric acids. After washing, mixing with alcohol and camphor a

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plastic is produced for rolling into sheets, sliced, dried and polished by hot pressing between metal sheets. These sheets still contain alcohol and can be cut and repressed to give patterned material or it can be extruded as plain sheet. Nitrocellulose cannot be injection molded because of its flammability. It is tough and moisture resistant for use as eyeglass frames and table tennis balls. If cellulose is pretreated with acetic acid, followed by more acid and its anhydride, acetate esters are formed giving cellulose triacetate. Complete acetylation would, produce an acetic acid content of 62.5%; in practice about 61% is usual. The material has a crystalline structure that is moisture-resistant, dimensionally stable, and a soluble in a limited range of solvents, especially methylene chloride with 10% methanol. Further treatment of the triacetate in solution in the presence of sulfuric acid splits off some acetic acid to give diacetate which is soluble in acetone, and compatible with a range of plasticizers that can be incorporated using a rugged mixer without solvent to yield molding powders especially suited to injection molding, e.g., tool handles. If butyric or propionic acids are included in the esterifying mixture, acetate butyrates and acetate propionates are formed. These, requiring less plasticizer, are tougher and more moisture resistant material for making automobile steering wheels.

Polyethylene Polyethylene has low density when polymerized at pressures 9,000 - 45,000 psi and high density when made with special catalysts at 250 - 500 psi. Low-density polyethylene softens 68° F lower than high-density polyethylene, which is more crystalline and stiffer. The rigidity characteristics and surface of high-density polyethylene are comparable with polystyrene. It feels like nylon, has a bursting strength three times that of low-density polyethylene, and withstands repeated exposure to 250° F, hence, it can be sterilized. Low-density polyethylene is used as film to make bags with thicknesses ranging from 0.25 to 7 mils for agriculture, building-site protection, packaging, and electrical insulation. Because of its stiffness, high-density polyethylene is used for large drums, gasoline tanks, bottle crates, and domestic appliances. It can also be produced as a foam. Polyethylene can be chlorinated in solution in carbon tetrachloride or in suspension in the presence of a catalyst. Below 55-60% chlorine, it is more stable and more compatible with many polymers, especially polyvinyl chloride, to which it gives increased impact strength. The low pressure process copolymerizes polyethylene with propylene and butylene to increase its resistance to stress cracking. Copolymerization with vinyl acetate at high pressure increases flexibility, resistance to stress cracking, and seal ability of value to the food industry. lonomers are ethylene polymers in which carboxyl groups are located along the ethylene chain. These acid groups are convened into salts of sodium, potassium, magnesium, or zinc to stiffen and toughen the plastic without destroying its thermoplastic character. As a result, unplasticized sheet has drawing characteristics superior to those of any other resin. lonomers are highly transparent, resistant to organic solvents, and maintain toughness at low temperatures. They are used in composite films with polyethylene and nylon because of their puncture resistance. They have strong natural adhesion to aluminum and are used in food packaging and as injection moldings in the shoe industry. Polypropylene is made by the polymerization of propylene. Stronger and more rigid than 280

Chemical Processes

polyethylene, with a harder surface, it softens 50 to 70° F higher, and is the lightest common plastic. It is more prone to oxidation than polyethylene unless appropriate stabilizers and antioxidants are added. Injection molding of it makes luggage, automotive panels and trims. Its fatigue resistance makes it useful for integral hinges. Polypropylene is used for fibers and film. The latter is extruded and develops its greatest strength when oriented by stretching biaxially i.e. along two axes at right angles. Film clarity is obtained by minimizing the size of crystals and by various additives. li is made in thicknesses as thin as 0.2 mil. Copolymers of propylene with minor amounts of ethylene are also used for making film. Methylpentene polymer, a light plastic, has a crystalline melting point of 464° F, form retention up to 392° F, transparency of 92%, and electrical properties similar to polytetrafluoroethylene. Its impact strength is greater than polystyrene and polymethyl methacrylate; it is resistant to alkalies, weak acids, and non-chlorinated solvents. It may be injection molded into implements for food packaging and preparation, medical care, and non-stick coatings. Vinyl chloride is made from ethylene or acetylene and chlorine. The polymer, polyvinyl chloride is made plastic by calendering, extrusion, and molding. The most commonly used plasticizer is dioctylphthalate, but adipates may be used for special resistance to temperature change. Applications of flexible polyvinyl chloride are clothing, flooring, wire insulation, home furnishings, plumbing, toys, and steel sheet covering. Copolymers of vinyl chloride, containing 5 to 40 percent vinyl acetate made by the inclusion of vinyl acetate in the polymerization process, have lower softening points and flow more easily than polyvinyl chloride. They are soluble in ketones, such as acetone, and certain esters for making film from solutions. They are used for phonograph records, rigid clear sheeting, and molding powders, Acrylic Acrylic is a generic name for derivatives of acrylic acid, of which methyl methacrylate is the most important. Polymerization is controlled to produce chain length of 800 to 3,000 monomer units. A small amount of plasticizer such as dibutyl phthalate may be added before bulk polymerization to assist in deep molding. The outstanding property of polymethyl methacrylate is 92% transparency; resistance to ultraviolet radiation from fluorescent lamps and ability to be fashioned by deep drawing or injection molding. It is used for airplane canopies, dentures, optics, and light covers of various colors. A use is for internally illuminated signs in which any color can be introduced. Its dimensional stability recommends it for many optical uses. Acrylics are modified by copolymerization to improve impact strength at the loss their extreme transparency. An example is acrylic-modified polyvinyl chloride sheet, which is tougher than acrylonitrile-butadiene-styrene and polycarbonate and is suitable for corrosion-resistant pans, aircraft parts and materials handling equipment. Polytetrafluoroethylene and fluorinated ethylene-propylene are the only resins composed wholly of fluorine and carbon. The polymer consists of fluorine atoms surrounding the carbon chain as a sheath, giving a chemically inert and relatively dense product from the strong carbon-fluorine bonds. Polytetrafluoroethylene must be molded at high pressure. Fluorinated ethylene-propylene can be injection molded and extruded as thin film. Both plastics have exceptional heat resistance 281


and very low friction coefficients. They are used for seal rings, non-lubricated bearings, packings, and electrical applications. Styrene Styrene is polymerized to the clear resin: polystyrene by: mass-block, continuous mass process, or suspension polymerization in water. The mass-block method, polymerizes using cells alternately filled with monomer and a cooling medium. Continuous polymerization uses a tower with cooling zones and a heated base from which the polymer is extruded. Polystyrene is an injection material that is hard, brittle, flammable, transparent, good insulator, but softens in boiling water. High-impact polystyrene is made by dissolving styrenebutadiene rubber in styrene and polymerizing the styrene. Acrylonitrile-butadiene-styrene polymers are similar in structure, but the acrylonitriie hardens the polymer. Minute rubber particles act as stress-relief centers, making it good for large objects: luggage or car body parts. It can be chrome plated, foamed, injection molded, blown, and alloyed with other plastics. Formaldehyde Polymers Formaldehyde polymerizes to paraformaldehyde, a stable polymer of high molecular weight. It is one of the strongest and stiffest thermoplastics. It can be injection molded and extruded. It is used in automotive safety steering columns because of fatigue resistance, and in snap-fit assemblies because of its impact strength and elastic recovery. It is moisture and abrasion resistant with good electrical properties over a wide temperature range. When glass-fiber-filled, it has exceptional resistance to creep. Nylon and Condensation Polymers Nyion-6.6 is made by heating amine and acid in an autoclave from which it is extruded onto a chilled drum and segmented. It has: high melting point, strength, stiffness, toughness, and chemical resistance. These properties make it a substitute for metal used for gears, oil seals, bearings, and structural components. Extruded film is used for boil-in-bag packaging. Other nylons are made by varying the molecular length of the diamines and the dibasic acids: Nylon-6.10 uses sebacic acid (10 carbon atoms), nylon-11 uses an acid from castor oil, and nylon-12 uses butadiene. These variations decrease moisture absorption. Other variations use amines with a ring structure, e.g., the aromatic nylons to give polymers with softening points above 577° F. Polyethyleneterephthalate This is a polyester made from glycol and dimethyl terephthalate by ester interchange. The reaction produces methanol instead of water for displacement by ordinary esterification. The product is extruded as a transparent amorphous film. If it is stretched biaxially at 176° F, it is still amorphous and is used for shrink-wrapping food stuffs and medical accessories by momentarily reheating it above the stretch temperature. If the film is biaxially stretched to three or four times its original dimensions, at a higher temperature, it crystallizes and develops very high tensile strength (25 kpsi) and dimensional stability.

282

Chemical Processes

Polycarbonates Are long-chain linear polyesters of carbonic acid and dihydric phenols, such as bisphenol A, This faintly amber, transparent plastic has toughness, tensile strength, ductility, and dimensional stability from 60 to 300° F. It is injection molded, blow molded, and extruded as a metal substitute with good electrical insulating properties. It is used for tool housings, safety helmets, computer parts, and vandal-proof windows. Polyimides Are made by a two-step reaction of dianhydride (tetrabasic acid with two molecules of water removed) with an aromatic diamine giving first a polyamic acid that is converted by heat or catalysts to high molecular weight linear polyimides. They are used as film, laminating resins, adhesives, and molding compounds. They are the best organic materials for high temperature insulators, capacitors, and bearings. If one amino group in o-phenylenediamine is converted to an amide group by formic acid, the intermediate; benzimidazole is formed. This reaction, conducted with a wide range of reactants, produces resins (polybenzimidazoles) used as high-temperature adhesives for laminates in the aerospace industry. Heat insulation is made by including tiny bubbles of silica and alumina fibers for reentry vehicle fuel cells, and nuclear reactors. Nose cone ablative material is made by incorporating phenolic microballoons and carbon fibers in the plastic.

7.2.8 Paints and Varnishes Paint is a pigment in a binder hiding what is underneath it. Inorganic pigments are insoluble, metallic compounds whose colors come from the energy levels of the pigment. Organic pigments are compounds containing molecules with atoms of the desired properties. Paint is manufactured in batches up to 2,500 gallons; the binders are composed of polymeric resins in a solvent. The pigments are ground to colloidal size in ball mills (rotating containers containing the material being ground and steel or ceramic balls), or sand grinders, which circulate a suspension of sand in paint through a rotor assembly at high speed. Paint must be uniform in color, flow, and have other physical properties. Driers, fungicides, and tint bases are added during thinning. The paint is measured for hue, brightness, and chrome. White pigments and extenders provide hiding power by scattering light; hue is provided by pigments and toners that absorb light of certain wavelengths. White Pigments White lead (2PbCO3 Pb[OH]2) has been manufactured for over 300 years by subjecting lead sheet to acetic acid fumes and carbon dioxide for several months. Sulfate of lead (PbSO4 PbO) is manufactured by vaporizing lead and sulfur. Zinc oxide (ZnO) results from the reaction of zinc vapor and oxygen. Zinc sulfide (ZnS) is formed by precipitation from an aqueous solution and heating to a high temperature. Lithopone (ZnS + BaSO) is formed by precipitating zinc sulfate (ZnSO4) and barium sulfide (BaS) together. Antimony trioxide (Sb2O3) is produced by roasting antimony in air. Titanium dioxide (TiO2) requires the removal of iron from ilmenite ore, FeTiO,

283


after which it is heated with small amounts of aluminum, antimony, silicon or zinc oxide to produce white pigments with suitable properties.

Black Pigments Most black pigments are made of carbon black formed by depositing carbon from a smoky flame of natural gas on a metal surface, Lampblack is made similarly by burning oil. Bone blacks are made from charred bones. Graphite occurs naturally or can be prepared from coal in electric furnaces. Mineral blacks come from shale, peat, and coal dust. Iron oxide blacks are found in nature or prepared. Blue lead sulfate is a pigment for priming. Of these, carbon black is superior.

Colored Pigments Colored pigments are grouped according to their position in the visible spectrum. Mineral varieties dominate the red and blue ends with organic varieties in between. Common red pigments are red lead, iron oxide, cadmium reds, cuprous oxide, and various organics. Red lead (Pb3O4) is a protective coating for steel. It is made by heating metallic lead or lead oxide. Iron oxide (Fe2O3) occurs naturally by weathering of silicate rocks and was used prehistorically. Other ocres are the sennas composed of 30 to 75% iron oxide ranging from yellow-brown to reddish-orange depending on the variety and the degree of calcination. Timbers have high manganese dioxide content and tend toward brown coloration. Iron oxide ores include hematite ores, such as Spanish oxide and Persian Gulf oxide, magnetite (black), limonite (yellow), siderite (brown), and pyrites (dark brown). Synthetic iron oxide, made by calcinating ferrous sulfate (FeSO4), ranges from light Turkey red to dark Indian red; calcination in lime (CaO) produces a mixture of ferric oxide and calcium sulfate (CaS04) known as Venetian red. Miscellaneous inorganic red pigments include cadmium reds, which rely on the mixture of cadmium sulfide (CDS) and selenide (CdSe) to produce colors ranging from light red to maroon, and cuprous oxide (Cu2O), a fungicide. Organic red pigments include naturally occurring carmine and madder and synthetics. Synthetics are expensive but can have an infinite variety of hues by changing the molecular structure. Yellow and orange pigments are obtained from metallic salts and from organic compounds. Chrome yellows and oranges are low-cost, bright, and stable pigments that display a considerable range of hues. Consisting of various proportions of lead chromate (PbCrO4), lead sulfate (PbSO4), and lead monoxide (PbO), all turn brown when exposed to sulfide gases because of the formation of lead sulfide (PbS). Molybdate oranges are made from lead chromate precipitated with lead molybdate (PbMoO4) and lead sulfate (PbSO4). Zinc yellow has a greenish cast because of a high content of chromic oxide. It is light fast, rust inhibitive, and sulfide resistant, Basic zinc chromate (5ZnO CrO3) is an undercoat. Cadmium yellow and oranges are formed by diluting yellow cadmium sulfic (CDS) with white zinc sulfide (ZnS) and barium sulfate (BaSO4), using small amounts of red cadmium selenide (CdSe) to impart the orange coloration. Blue and green pigments are mostly synthetic soda produced by fusing china clay in a mixture of sulfur, sodium sulfate, and an organic reducing agent such as rosin. The glassy product is pulverized, leached free of sodium sulfate, and size-separated by sedimentation. The most widely used blue pigments are iron blue that contain various amounts of iron, ammonium and sodium ions, and hydration. Chinese blue has a greenish-blue tint; Milo blue tends toward the red, Phthalo284

Chemical Processes

cyanine pigments, with a rather complicated organic structure, are reproducible, light-fast, brilliant but expensive to produce. Binders A surface coating protects the substrate against abrasion, moisture, light, and corrosion. The binder for the pigment and extenders is fluid before application and rigid soon after. Natural binders range from gum arabic to fish oil. The first varnishes were solutions of natural resins, having transparency, hardness, amorphous structure, and little permanence. Synthetic resins form the heart of the paint industry. The two main types of synthetic resins are condensation polymers and addition polymers. Condensation polymers, formed by condensation of like or unlike molecules into a new, more complex compound, include polyesters, phenolics, amino resins, polyurethane, and epoxies. Addition polymers include polyvinyl acetate, polyvinyl chloride, and the acrylates, Condensation Polymer Resins Alkyds are the most widely used protective-coatings at 1-million pounds annual world consumption. Brittle and insoluble in common solvents, they are manufactured with a plasticizer. Manipulating the molecular structure produces alkyds with the desirable properties. Phenol (C6H5OH) reacts readily with aldehydes to form oil soluble compounds called phenolic resins that dry rapidly, are hard, chemical and abrasion resistant, but they tend to yellow with age. Condensation of urea (HjNCONH^ or melamine (C p $11 with formaldehyde (HCHO) produces the amino resins which are non-yellowing, alkali resistant and have good adhesive properties for use in coatings. These amino resins contain an alcohol as a third component. Both polyurethanes and epoxy resins are produced using complex organic reactions. Polyurethane coatings dry hard and inert on a substrate; epoxy resins have qualities of toughness, adhesion, chemical resistance, rigidity, and thermal resistance. Silicones are produced by attaching organic groups to a silicon atom. They are hard, tough, clear, glossy, heat, weather and chemical resistant. Addition Polymers Ethylene, a simple, unsaturated organic molecule, is made into translucent, inexpensive, waxy polyethylenes at high pressures. When polyethylenes are applied to substrates, the resulting film is resilient and resistant to acids and oxidizers. A synthetic addition polymers that has largely replaced natural resins is polyvinyl acetate. It is a clear, transparent resin that softens below the boiling point of water. It is sensitive to water, soluble in many organic solvents and has good adhesion properties. Vinyl resins are dissolved or suspended in an organic medium, like the natural resins, or polymerized and marketed as an aqueous latex emulsion. Polyvinyl chlorides are not desirable as coatings. Clear, non-yellowing, and heat stable acrylic compounds, are used to produce acrylic emulsion paints. Their manufacture consists of dispersing the pigment in water and adding the latex with only moderate agitation.

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7.2.9 Petrochemical Processing 7.2.9.1 Overview Many chemical products are produced from crude oil. Initially, little chemistry was involved therefore the petrochemicals were not considered part of the chemical process industry. Today, materials ranging from specialized fuels, plastics and synthetics makes it part of the chemical processing. The petroleum refinery is where the chemical processing of oil begins. Topping and Hydroskimming Refineries The simplest plant is a topping refinery that prepares feedstocks for petrochemical manufacture or for production of industrial fuels. It consists of tankage, a distillation unit, recovery facilities for gases and light hydrocarbons, and supporting utilities (steam, power, and watertreatment plants). The range of products is increased by the addition of hydrotreating and reforming units comprising a hydroskimming refinery, which can produce desulfurized distillate fuels and high-octane gasoline. About half of the production is fuel oil.

Conversion Refineries More versatile is a conversion refinery consisting of the equipment found in topping and hydroskimming refineries with gas oil conversion operations such as catalytic cracking and hydrocracking units, olefm conversion plants such as alkylation or polymerization units, and, frequently, coking units for sharply reducing or eliminating the production of residual fuels. Two-thirds of the production of a modern conversion refinery may be unleaded gasoline, with the balance being high-quality jet fuel, LPG, low-sulfur diesel fuel, and a small quantity of petroleum coke. Many such refineries also incorporate solvent extraction processes for manufacturing lubricants and petrochemical units to recover high-purity propylene, benzene, toluene, and xylenes for further processing into polymers.

7.2.9.2 Basic Refinery Processes A refinery separates the many types of hydrocarbons present in crude oils into related fractions of chemically converted, separated hydrocarbon products, and recovers the wastes that are produced.

Fractional Distillation The primary process for separating the hydrocarbon components of crude oil is fractional distillation i.e. separation according to the boiling points of the components. These separated fractions are processed further by: catalytic reformers, cracking units, alkylation units, or cokers which have there own fractional distillation towers for its products. Modern crude oil distillation units are larger than those in the chemical process industry, producing up to 200,000 barrels per day of product.

286

Chemical Processes Figure

7.2-4

ShOWS

the

-/^

Condenser x~tf

operating principles of a modern crude oil distillation unit. Crude oil is pumped from tankage at ambient temperature through heat exchangers to raise its temperature to 248° F. A controlled amount of fresh water is introduced, and the mixture is pumped into the desalter, where it passes through an electrical field to separate the saltwater phase to prevent deposition on the tubes of the furnace and cause plugging. The desalted crude oil passes through additional heat exchangers and then through steel alloy tubes in a furnace. There it is heated to about 698° F - Salt Water depending on the type of crude oil,

Valve» Fuel Gas

Residue Fi

%- 7.2-4 Diagram of a Fractional Distillation Column

and the end products desired. A mixture of vapor and unvaporized oil passes from the furnace into the fractionating column, which is a vertical cylindrical tower up to 150 feet high containing 20 to 40 fractionating trays spaced at regular intervals. The most common fractionating trays are of the sieve or valve type. Sieve trays are simple perforated plates with small holes about 0.25 inch in diameter. Valve trays are similar, except the perforations are covered by small metal disks that restrict the flow through the perforations under certain process conditions. Oil vapors rise up through the column and tire condensed by a water or air-cooled condenser at the top of the tower. A small amount of gas remains uncondensed and is piped into the refinery fuel-gas system. A pressure control valve on the fuel-gas line maintains fractionating column pressure (~ atmospheric). Part of the condensed liquid, called reflux, is pumped back into the top of the column and descends from tray to tray, contacting rising vapors as they pass through the slots in the trays. The liquid progressively absorbs heavier constituents from the vapor and gives up lighter constituents to the vapor phase. Condensation and reevaporation takes place on each tray. At equilibrium, there is a continual gradation of temperature and oil properties throughout the column, with the lightest constituents on the top tray and the heaviest on the bottom. The use of reflux and vapor-liquid contacting trays distinguishes fractional distillation from simple distillation columns. As shown in the figure, intermediate products are withdrawn at several points from the column. In addition, modern crude distillation units employ intermediate reflux streams. Typical boiling ranges for various streams are: light straight-run naphtha (overhead), heavy naphtha (top sidestream), 195 to 330° F; crude kerosene (second sidestream), 300-475 °F; light gas oil (third sidestream), 420 to 600° F. Unvaporized oil entering the column flows downward over stripping trays to remove any light constituents remaining in the liquid. Steam is injected into the bottom of the column to reduce the partial pressure of the hydrocarbons and separation products. Typically a 287


single sidestream is withdrawn from the stripping section to give a heavy gas oil, with a boiling range of 545 -700° F. The residue from the bottom of the column is suitable for blending into industrial fuels. Alternately, it may be further distilled under vacuum conditions to yield quantities of distilled oils for manufacture into lubricating oils or for use as a feedstock for a gas oil cracking process. Vacuum distillation resembles fractional distillation except the column diameters are larger to give comparable vapor velocities at a pressure of 50 to 100 mm Hg (absolute) achieved by vacuum pump or steam ejector. Vacuum distillation reduces the boiling temperature for processing materials below that boiling temperature at atmospheric pressure, thus avoiding thermal cracking of the components. Firing conditions in the furnace are adjusted so that oil temperatures do not exceed 800° F, The residue (bitumen) remaining after vacuum distillation, is used for road asphalt, residual fuel oil, or a feedstock for thermal cracking or coking units. Superfractionation is an extension of distillation using smaller diameter columns and 100 or more trays to achieve reflux ratios exceeding 5:1. This equipment separates a narrow range of components such as of high-purity solvents, e.g., isoparaffms or individual aromatic compounds for use as petrochemicals. Absorption Absorption recovers valuable light components such as propane/propylene and butane/ butylene as vapors from fractionating columns. These vapors are bubbled through an absorption fluid, such as kerosene or heavy naphtha, in a fractionating-like column to dissolve in the oil while gases, such as hydrogen, methane, ethane, and ethylene, pass through. Absorption is effectively performed at 100 to 150 psi with absorber heated and distilled. The gas fraction is condensed as liquefied petroleum gas (LPG). The liquid fraction is reused in the absorption tower. Solvent Extraction Solvent extraction removes harmful constituents such as heavy aromatic compounds from lubricating oils to improve the viscosity-temperature relationship. The usual solvents for extracting lubricating oil are phenol and furfural. Adsorption Certain highly porous solid materials selectively adsorb certain molecules. Examples are: silica gel for separation of aromatics from other hydrocarbons, and activated charcoal for removing liquid components from gases. Adsorption is analogous to absorption, but the principles are different. Layers of adsorbed material, only a few molecules thick, are formed on the extensive interior area of the adsorbent - possibly as large as 50,000 sq. ft./lb of material. Molecular sieves are an adsorbent that is produced by the dehydration of naturally occurring or synthetic zeolites (crystalline alkali-metal aluminosilicates). The dehydration leaves intercrystalline cavities into which normal paraffin molecules are selectively retained and other molecules are excluded. This process is used to remove normal paraffins from gasoline fuels for improved combustion. Molecular sieves are used to manufacture high-purity solvents.

288

Chemical Processes Crystallization

The crystallization of wax from lubricating oil fractions makes better oil. This is done by adding a solvent (often a mixture of benzene and methyl ethyl ketone) to the oil at a temperature of about -5° F. The benzene keeps the oil in solution and maintains fluidity at low temperature; the methyl ethyl ketone acts to precipitate the wax. Rotary filters deposit the wax crystals on a specially woven cloth stretched over a perforated cylindrical drum. A vacuum in the drum draws the oil through the perforations. The wax crystals are removed from the cloth by metal scrapers and solvent-washed to remove oil followed by solvent distillation to remove oil for reuse. 7.2.9.3 Conversion The separation processes separate the constituents of crude-oil based on physical properties. Conversion of one molecule into another greatly extends the usefulness of petroleum by extending the range of hydrocarbon products. Thermal Conversion The initial process for molecular conversion was thermal reforming (late 1920s). Thermal reforming at 950 - 1050°F and 600 psi produced gasolines of 70 to 80 octane and heavy naphthas less than 40 octane. Products were olefins, diolefms, and aromatic compounds that were unstable in storage and tended to form heavy polymers and gums, which caused combustion problems. According to the free-radical theory of molecular transformation, thermal cracking works, by heat-breaking the electron bond between carbon atoms in a hydrocarbon molecule to generate a hydrocarbon group with an unpaired electron. The negatively charged, free radical, reacts with other hydrocarbons, continually producing other free radicals via the transfer of negatively charged hydride tons (H). This chain reaction leads to a reduction in molecular size called "cracking," of components of the original feedstock. -»• Catalytic Conversion •n < nen c

- •

. _.*•

Reactor effluent Fractionator

to By 1950 a reforming process was ^ introduced using a catalyst to improve the yield '" cyclone vessel of the desirable gasoline components while minimizing the formation of unwanted material. stripper ,„„ stripper steam v In catalytic as in thermal reforming, a naphtha— caîy^ type material serves as the feedstock, but the Regenerator rip e reactions are carried out in the presence of f! Br r Standpipe Riser hydrogen, to inhibit the formation of unstable Reactor , , , , • • ' Regenerator unsaturated compounds that polymerize into Air < Standpipe higher-boiling materials. In most catalytic . L0wer reforming processes, platinum on aluminum Air Heater inlSon ^h Feed oxide is the catalyst. Small amounts of rhenium, A >. chlorine, and fluorine are catalyst promoters. Dispersion steam (

The high cost of platinum is overcome by its

289

Fig_

7.2-5 Schematic of a Catalytic Cracking Unit


long life and effectiveness. The principal reactions involve breaking down the long-chain hydrocarbons into smaller saturated chains while forming isoparaffins. Formation of ring compounds by cyclization of paraffins into naphthenes, also takes place, and the naphthenes are then dehydrogenated into aromatic compounds. The desirable end products are isoparaffins and aromatics, both having high octane numbers. In a typical reforming unit (Figure 7.2-5) the naphtha charge is first passed over a catalyst bed in the presence of hydrogen to remove any sulfur impurities. The desulfurized feed is mixed with hydrogen (about five molecules of hydrogen to one of hydrocarbon) and heated to 930 to 1000° F at 100 psi. Because heat is absorbed in reforming reactions, the mixture must be reheated in intermediate furnaces between the reactors. After leaving the final reactor, the product is condensed to liquid, separated from hydrogen and distilled to remove the light hydrocarbons. The product may be blended into gasoline without further treatment. Process parameters are set to obtain the required octane level (~90). In the process, minute amounts of carbon are deposited on the catalyst which reduces the product yield, but can be removed by batch burning. Continuous regeneration avoids periodic shutdowns and maximizes the high-octane yield. This employs a moving bed of catalyst particles that is circulated through a regenerator vessel, for carbon removal, and returned to the reactor.

Polymerization and Alkylation The light gaseous hydrocarbons produced by catalytic cracking are highly unsaturated and are usually converted into high-octane gasoline components by polymerization or alkylation. In polymerization, the light olefins, propylene and butylene, are induced to polymerize into molecules two or three times their original molecular weight using as the catalyst: phosphoric acid on pellets of kieselguhr. Pressures of 400 to 1,100 psi at 350 - 450°F produce polymer gasolines derived from propylene and butylene having octanes above 90. The alkylation reaction achieves a longer chain molecule by combining two smaller molecules - an olefin and an isoparaffin (usually isobutane). During World War II, alkylation became the main process for the manufacture of isooctane, a primary component for blending aviation gasoline. Two industrial alkylation processes use different acid systems as catalysts. In sulfuric acid alkylation, concentrated sulfuric acid of 98% serves as the catalyst for a reaction that is carried out at 35 - 45°F. Refrigeration is necessary because heat is generated by the reaction. The octane of the alkylates is 85-95. The chemical reactions with hydrofluoric acid as the catalyst are similar to those with sulfuric acid as the catalyst but higher temperatures (115°F) can be used, thus avoiding refrigeration. Hydrofluoric acid is recovered by distillation. Stringent safety precautions most be exercised when using this highly corrosive and toxic substance.

Hydrocracking The use of hydrogen from catalytic reforming was a far-reaching development, in the 1950s. By 1980, it had become so prominent that many refineries incorporate hydrogen manufacturing plants. Though using a feedstock similar to catalytic cracking, it offers even greater flexibility in product yields. The process can produce; gasoline, jet fuels, heavy gas oils, high-quality lubricating oils, or lighter oils by distilling the residues. 290

Chemical Processes

Hydrocracking is accomplished at lower temperatures (500 - 800° F) than catalytic cracking, but at higher pressures (1,000 - 4,000 psi). While hydrocracking catalysts vary widely, cracking reactions can be induced by silica-alumina materials. In units that process residual feedstocks, hydrogenation catalysts are: nickel, tungsten, platinum, or palladium. The catalysts do not require regeneration. isomerization The demand for aviation gasoline during World War fl was so great that isobutane from alkylation feedstock was insufficient. This deficiency was remedied by isomerization of abundant normal butane into isobutane using the isomerization catalyst: aluminum chloride on alumina promoted by hydrogen chloride gas. Commercial processes isomerize low-octane normal pentane and normal hexane to the higher-octane isoparaffin, using a platinum catalyst in the presence of hydrogen. Hydrogen as a catalyst inhibits undesirable side reactions. This reaction is followed by molecular sieve extraction and distillation which excludes low-octane components from the gasoline blending pool, and does not produce a product of sufficiently high octane for unleaded gasoline, Visbreaking, Thermal Cracking, and Coking Since the war the demand for gasoline, jet, and diesel fuels has grown, while the demand for heavy industrial fuel oils has declined. Furthermore, many new oil finds have yielded heavier crudes, therefore the need to convert residue components into lighter oils for feedstock for catalytic cracking. As early as 1920, large volumes of residue were processed in thermal cracking units. The furnace residence time was controlled to prevent clogging the furnace tubes. The heated feed was charged in a reaction chamber, at a pressure high enough to permit cracking of the large molecules but limit coke formation. Afterward, the process fluid was cooled to inhibit further cracking and charged to a distillation column for separation into components. These visbreaking units typically converted about 15% of the feedstock to naphtha and diesel oils and produced a lower-viscosity residual fuel. Thermal cracking units provide more severe processing and often convert as much as 50 to 60% of the incoming feed to naphtha and light diesel oils. Coking is severe thermal cracking. The residue feed is heated to about 890 - 970° F in a furnace with very low residence time and is discharged into the bottom of a large vessel called a coke drum for extensive and controlled cracking. The cracked lighter product rises to the top in the drum and is drawn off to the product fractionator for separation into naphtha, diesel oils, and heavy gas oils for further processing in the catalytic cracking unit. The heavier product settles in the drum and, because of the retained heat, cracks ultimately to coke, a solid carbonaceous substance akin to coal. Once the coke drum is filled with solid coke, it is removed from service and replaced by another coke drum. Decoking is a routine daily occurrence accomplished by a high-pressure water jet. First the lop and bottom heads of the coke drum are removed then a hole is drilled in the coke from top to bottom. A rotating stem is lowered through the hole, spraying a jet high-pressure water sideways

291


to cut the coke into lumps that fall to the bottom of the drum for shipment to customers. Coking cycles consists of 24 hours to fill the drum and 24-hours cooling, decoking, and reheating. Cokers produce no liquid residue but yield up to 30% coke. Much of the low-sulfur product is used for electrolytic electrodes for smelting of aluminum. Lower-quality coke is burned as fuel mixed with coal, Purification Petroleum products must be purified of sulfur compounds such as hydrogen sulfide (H2S) or the mercaptans ("R"SH), where "R" is the hydrocarbon radical forming complex organic compounds. Besides the bad odor, sulfur compounds reduce the effectiveness of antiknock additives, interfere with the operation of exhaust-treatment systems, and corrode diesel engines. Other undesirable components are nitrogen compounds, that poison catalytic systems, and oxygenated compounds leading to color formation and product instability. The principal treatment processes are: i) sweetening, 2) mercaptan extraction, 3) clay treatment, 4) hydrogen treatment, and 5) molecular sieves, 1) Sweetening processes originally used sodium plumbite as the catalyst to oxidize mercaptans into more innocuous disulfides, which remain in the product fuels. This inexpensive process increased the total sulfur content in the product, hence it was replaced by copper chloride slurry as the catalyst used for making kerosene and gasoline. The oil is heated and brought into contact with the slurry while being agitated in a stream of air that oxidizes the mercaptans to disulfides. The slurry is allowed to settle and is separated for reuse. The temperature is sufficient to keep the water, formed in the reaction, dissolved in the oil, so the catalyst remains properly hydrated. After sweetening, the oil is water-washed to remove traces of catalyst and dried by passing through a salt filter. 2) Mercaptan extraction is used to reduce the total sulfur content of the fuel. When potassium isobutyrate and sodium cresylate are added to caustic soda, the solubility of the higher mercaptans is increased and they can be extracted from the oil. To remove traces of hydrogen sulfide and alkyl phenols, the oil is pretreated with caustic soda in a packed column or other mixing device. The mixture is allowed to settle and the product water washed before storage. 3) Clay treatment uses natural clays, activated by roasting or treatment with steam or acids, to remove traces of impurities by an adsorption process to remove gum and gum-forming materials from thermally cracked gasolines in the vapor phase. A more economical procedure, however, is to add small quantities of synthetic antioxidants to the gasoline. These prevent or greatly retard gum formation. Clay treatment of lubricating oils is widely practiced to remove resins and other color bodies remaining after solvent extraction. The treatment may be by contacting the clay directly with the oil while heated and filtering the clay, or by percolating the heated oil through a large bed of active clay adsorbent. The spent clay is discarded, or regenerated by roasting. 4) Hydrogen treatment (hydrofmishing, hydrofining, or hydrodesulfurization), are processes for removing sulfur compounds. The oil and hydrogen are vaporized, and passed over a catalyst (e.g., tungsten, or nickel) at 500 - 800°F and 200 - 1,000 psi. Such parameters are chosen according to the sulfur removal requirements without degrading the oil. The sulfur in the oil converts to hydrogen sulfide, which is removed by absorption in diethanolamine which can be reused by heating

292

Chemical Process Accident Analysis

with the hydrogen sulfide and provide high purity sulfur, 5) Molecular sieves (dehydrated zeolite) purify petroleum products with their strong affinity for polar compounds such as water, carbon dioxide, hydrogen sulfide, and rnercaptans. The petroleum product is passed through the sieve until the impurity is sufficiently removed after which the sieve may be regenerated by heating to 400 - 600° F.

7.3 Chemical Process Accident Analysis Similarities between Nuclear and Chemical Safety Analysis Nuclear power production Table 7.3-1 Hazard Criteria involves bringing fissionable Question Comment material together to react nuclearly, Is there a possibility of Many of the explosions in chemical removing the heat, converting the nitrating a compound? processing are the result of nitrating be it cellulose, tributylphosphate (to form red heat to steam to drive a turbooil), or ammonia to form fertilizer. generator, and managing the wastes. Are toxic materials This was the cause of the Bhopal Chemical process production involbeing processed? accident, and the less disastrous Seveso ves bringing molecules together to accident. react chemically, removing or Are combustible If these can be released and dispersed as providing heat, controlling and powders or vaporizing a cloud an explosion can result. For liquids processed? example, there have been severe confining the reaction, and at bread flower mills. explosions managing the wastes. Both nuclear Are high temperatures If these are liquid at high pressure and and chemical reactions involve involved that may cause temperature and the confinement fails Quids, hence, both use very similar combustible liquids to they will flash to vapor and could equipment, therefore similar safety potentially explode. vaporize? analysis methods should apply to Are caustic materials If these are released and contact people either as a vapor or liquid severe health processed? both. hazards result. For example, uranyl For historical and regulatory fluoride forms hydrofluoric acid in the reasons, a PSA of a nuclear power lungs. plant begins with the system analysis to determine the ways that an upset condition could occur, its probability of occurrence, and the consequences to the public if it occurred. A PSA of chemical processing tends to reverse this procedure1 by using scoping calculations of the consequences to determine if the hazard to workers and public is significant. If so, then to work backward to determine the process upsets and their likelihood that could cause these consequences. This approach has the advantage of reducing the number of process upsets that must be examined. In a nuclear plant, the hazard has one location - the core; a chemical plant, hazards have many locations. In a nuclear plant, the hazard is exposure to radiation and fission products; in a

r

Private telephone conversation between Lester Wittenberg, CCPS and Ralph Fullwood,

1997. 293

Analyzing Chemical Process Safety Systems Table 7.3-2 Objectives for Chemical PSA 1, Determine Risk Potential. The objective is to determine the possibility of significant risk of injury to workers or the public, or risk to the company's good name. It is done by bounding, consequence analyses and approximate frequency estimates, primarily for company protection. 2. Protect Workers and the Public. The reasons may not be entirely altruistic because worker injury is detrimental to production. Furthermore, we are the workers and wish a safe working environment free of immediate or latent injury. This requires detailed analysis of the process systems to estimate frequency of failure and the consequences that could result. Generally if the workers are safe, the public is safe. 3. Detect Financial Risks. In addition to physical injuries, a company may be injured by the perception of injury that result in law suits, drop in stock price, and reduction in sales. A detailed analysis (2) will assess vulnerability but it does not directly address the perception factor. A case in point is TMI-2 which complied with 10 CFR100, had no injuries and no deaths, but the company was driven to near-bankruptcy. Similarly with Bhopal and Union Carbide, although there were deaths. 4, Prioritize Safety Improvements. This uses the detailed analysis (2) to identify items having high risk importance. Engineering analysis identifies and costs candidate improvements which are selected on the basis of risk reduction for a given cost. 5, Legal Compliance. Bounding (1) or detailed analyses (2) may be used to show compliance with national and regional measures, e.g., the PSM Rule. 6. Emergency Planning. A scoping (1) or detailed (2) PSA may be used to specify the emergency actions needed for emergency response zones about the plant. The use of on-site personnel, and their integration with local, state, and national groups and plans needs consideration. ______ 1. Plant Availability. A detailed PSA (2) may be used to analyze the effects of test and maintenance on plant operability through improved scheduling, component reliability improvement, and improved procedures. The costbenefit of stocking vs warehousing of feed materials and spare parts may be done to find an optimum.

chemical plant, the hazard is exposure to many different chemicals with different hazardous effects to the workers and public thus a much larger range of hazards and locations must be considered, hence, the benefit of screening the hazards. Is a PSA Needed? Table 7.3-1 lists questions, based on experience, which, answered in the affirmative, indicate hazards. The first question deals with the possibility of forming a nitrated compound. While not all explosives contain nitrogen, these have had a bad history. The basis for the second question is the Bhopal accident where an exothermic pesticide was being processed. Similarly, chlorine, while less toxic has been used with devastating results in warfare (Ypres). Communities are occasionally evacuated when chlorine is spilled. The third question is to point out that benign combustible materials, finely divided and dispersed, as a cloud, may conflagrate. The fourth question relates to the fact that liquids, under pressure and above their critical temperature, can flash to vapor if the pressure is released by vessel rupture or trip of pressure relief. Of course, an ignition source is needed to cause fire or explosion, but sources are usually present in one form or another. The fifth question deals with materials, while not poisonous, can injure flesh with which it comes in contact. This list, while not exhaustive, highlights hazards that may cause accidents. Table 7.3-2 lists some objectives for performing PSA on chemical process systems. Objective 1 is to determine if a process or plant has sufficient risk to justify a detailed analysis. This scoping analysis may be performed with a HAZOP (Section 3.3.4) or an FMEA (3.3.5) with either 294


analysis held to systems levels and bounding consequences. If it turns out that serious risk concerns exist, then the detailed analysis (2) is needed. Here the depth of analysis is controlled according to other objectives. If the purpose is legal (5) the depth is that required by the law; if the purposes are financial exposure, a detailed analysis may not be necessary and a scoping analysis may be sufficient. To use PSA for purposes 2, 4, 6, and/or 7, a detailed PSA is needed possibly supplemented in specific areas of interest.

7.3,1 Scoping Analysis The purpose of a scoping analysis is to determine, under worst case assumptions, if there is a risk that can cause injury, death or financial impact to the public, workers, company, or environment. The PSA begins by identifying the hazards, their physical and chemical properties, the confinement, conditions and distance for transport to a target, estimating the effects on the target, and comparing these effects with accepted criteria. 7.3.1.1 A Nuclear Scoping Analysis: WASH-740 It was stated earlier that PSAs for nuclear and chemical processes differ by preceding a chemical PSA with a scoping analysis that is omitted for a nuclear PSA. This is not true, WASH740 performed this purpose for a hypothetical plant. Originally, nuclear power was a government monopoly in the U.S. With Eisenhower's "Atoms for Peace," electric utilities were encouraged to use nuclear energy, but the utilities were hesitant because of the unknown risk. The Price-Anderson Act of 1957 capped the utility liability. In an attempt to scope the hazard, WASH-740 (1957) was prepared by BNL which estimated, under worst conditions, for a medium sized plant in or near a large city, an accident could cause 43,000 injuries, 3,400 deaths and $7 billion property damage. A reanalysis was performed in 1965 that concluded that the containment building eliminated risk to the public. It was later argued that the molten core would melt through the containment and an atmospheric release would occur." While WASH-740 indicated the accident potential, the question that it did not answer was the probability of an accident. The Reactor Safety Study (WASH-1400) was conducted for this purpose. Nevertheless, WASH-740 indicated the worst-case hazard of nuclear power, and the need for detailed PSAs of nuclear power plants. Since plants proposed for construction are sufficiently like the hypothetical plant in terms of fission products subsequent scoping analyses are not needed before the detailed PSA,

s

It may be noted that in the case of TMI-2, the core partially melted but did not get out of the pressure vessel. In the case of Chernobyl, there was no containment in the U.S. sense and what confinement there was, was disrupted by the nuclear excursion (like an explosion), 295


7.3,1.2 Performing a Process Scoping Analysis Preparing a Spreadsheet for Toxic Hazards Figure 7.3-1 outlines steps in the scoping Hazardous Material process. However, if this information is to be 1) Identification gathered, it should be in a convenient form such as 2) Quantities and Locations 3) Environmental Conditions collecting the data as a computer file in a notebook 4) Confinement personal computer. The file may be a word 5) Type of Hazard: Toxicity, Explosion, and/or Fire Comparison with Guidance processor, a spreadsheet, or a database. If the input 6) 7) Need for Detailed PSA? is into a word processor such as WordPerfect or Fig. 7.3-J Process Scoping Steps Word, it may be in table format. Very similar but with greater computational capabilities is a spreadsheet such as Excel or QuatroPro. A database program such as Access or dBase allows even greater flexibility in storage, formatting, and printing the report, but has less direct access to the data, and computational capabilities. A preferred method is inputting the data into a spreadsheet because of the ease in performing the calculations and the flexibility regarding the number of columns which may be off the screen but accessible by scrolling. Table 73.1-1 A Spreadsheet for Scoping Analysis Data

I Hazard Name/

2

3

Quantity/ Location phase

4 Confinement

6

5 Temperature

Pressure

CAS

Chlorine/ 2,200 lb/ Plan 1234 0.25 inch Ambient 7782-50-5 liquid

Location BB12

300 psi

thick steel vessel

7

8

9

Chemical Location Reaction and Amount of Reactants Inhalation None NA needed Type of Hazard

10

Hazard Criterion/ Scenario

TQ: 1500 lb/ Vessel rupture liquid flashes to vapor to injure workers by inhalation

Table 7.3.1-1 shows spreadsheet headings and a row of representative data. Column 1 identifies the hazard and its CAS (Chemical Abstract Service number).' The

' The chemical companies maintain chemical properties sheets including hazardous quantities. A general listing of companies on the Internet can be reached at web site: http://www.neis.com/ehemical_compames.html. The U.S. Department of Health and Human Services publishes the "NIOSH Pocket Guide to Chemical Hazards," available from NIOSH Publications Mail Stop C-13,4676 Columbia Parkway, Cincinnati, OH 45226-1998, phone 1800-35-NIOSH or on the Internet: http://www.cds.gov/niosh/homepage.html.

296


hazard identification involves judgment as to what can be a hazard. In this example, chlorine was identified as a hazard. It is a well known poison because it was used at Ypres in World War I with devastating effect. It is listed in Table 1.9-1 that also gives its CAS. Column 2 shows the quantity of material at a particular location in the plant and the phase it is in (solid, liquid, or gas). Column 3 gives the floor plan coordinates of the location of the material. Column 4 indicates how the hazard is confined. If it is a gas it will be in a closed container of sufficient strength to withstand the pressure. This may be expressed in terms of the wall thickness and material. If it is condensed to liquid phase, it will be under pressure; if it is a liquid al atmospheric pressure, it may be in a tank that is open at the top. Solids may be confined depending on whether or not they are powdered, granular or block. Table 7.3-2 Some Toxicology Sources Column 5 lists the Source Comments or Location normal temperature that the Table 1.9-1 in this book Thresholds for triggering the PSM rule chemical will experience as CRC Handbook, 1979 "Limits for Human Exposure to Air well as the upper and lower Contaminants" ranges. Temperature is "NIOSH Pocket Guide to See footnote t, page 298 in this book important because chemical Chemical Hazards" reactions go exponentially These are available on the Internet. Usually you Material Safety Data with temperature. The Sheets for the chemical's type http://www.xxx.com, where xxx is the range of variation may manufacturer manufacturer's name. If this doesn't work go to a search engine or try http://siri.org/msds/ for a indicate possible changes of general directory to chemical manufacturers. state Oral reference doses by EPA's IRIS (Integrated Risk Information System) Column 6 provides iittp://www.epa.gov/ngispgm3/iris/ chemical name for 535 the operating pressure and substances peak pressures that the DOE Chemical Safety trttp://dewey.tis.eh.doe.gov/web/chem_safety/ process may go to, Program This web site provides principles, chemical incidents in the DOE and hypertext connection to Column 7 lists the toxicity data. type of hazard that is being http://www.osha-slc.gov/SLTC/PEL/Jndex.html Permissible Exposure considered. If the chemical Limits (PELS) is toxic then the release and American Conference of Governmental Industrial ACGIH dispersion to the workers Hygienists, http://www.acgih.org/This web site and public is the hazard. connects with a number of publications some of which are listed below. Another simple hazard is a Sax, 1987 Hazardous Chemicals pressure vessel rupture due Desk Reference to over pressure. A steam Casarett, 199! Casarett and Doull's vessel rupture may scald Toxicology : the Basic workers and injure them Science of Poisons with shrapnel. Many people Dangerous Properties of Sax, 1989 died in the last century from Industrial Materials boiler explosions. The ves297


sel may have pressure valves, but if the contents are poisonous, as was the case at Bhopal, the discharge through relief channels may be hazardous. A complex example may occur if the contents react chemically with something else to release energy or form a poisonous substance. An example is the release of sodium into water. Column 8 gives the chemical reaction that may occur, whether it is exothermic and poisonous, Column 9 indicates the location and names of other reactant materials Column 10 is used to list hazard / 3 99 4.1 criteria from sources such as given in 8 Table 7.3.1-2. Inhalation limits often ppm = ™ (7.3-1) are given in either units of parts-permolecular weight of chemical million (ppm) in air or milligrams (mg) of the chemical per cubic meter. Equation 7.3-1 gives the connection between these units. Including Fire and Explosive Hazards in the Spreadsheet Some chemicals can react with themselves or with other chemicals to burn or explode to release their chemical energy. The distinction between burning or exploding depends on the rate of reaction according to the following definitions: *

»

•

Fire, burning, or combustion is a chemical reaction that takes place so slowly that no pressure wave is produced. A flame may be visible, temperatures reaching 1,000s of degrees may be produced. The damage mechanisms are: burns, suffocation by depleting oxygen, poisoning from combustion product production (e.g., carbon monoxide), or mechanical damage from falling structure or steam formation in closed vessels. Deflagration is burning that takes place subsonically, hence, no shock front is produced. The damage mechanisms are: physical destruction from the pressure wave, collateral damage from falling structures, and burns of humans. Suffocation and poisoning are not usually associated with a deflagration because of its short duration. A substance that normally burns in air can produce a deflagration if it is finely suspended in air. Examples are: suspended coal dust, flour, gasoline, kerosene oil, and metal powder. In these examples the common reactant chemical is oxygen in the air. A mixture of chemicals such as compose black powder can produce a deflagration without air. Deflagrations may be caused by mixing one chemical with a reactant chemical. In such cases, safety is provided by identifying the reactant and isolating it from the reactee. Percent limits of inflammability of gases and vapors in air are given in CRC (1979, and later editions). Explosion is burning that takes place sonically, hence, a shock front is produced. The damage mechanisms are: physical destruction from the shock wave, collateral damage from falling structures, and human burns. Suffocation and poisoning are not usually associated with an explosion because of its short duration. A chemical explosives such as nitroglycerine, trinitrotoluene, dynamite, and others were discussed in Section 7.2.6.

298


Evaluation of the Scoping Analysis Spreadsheet The MSDS from the chemical manufacturer identifies hazards for entry in the spreadsheet in columns 8 and 10. This is performed for all chemicals that are associated with the process, if the analysis is limited to a process, or for a plant. The spreadsheet may be filled out variously according to convenience and effectiveness. It is practically impossible to get all needed information from documentation alone. A plant walk-through is advised for viewing operating conditions as they exist, for interviewing operators about the risk concerns that they have, and about the operability of safety and mitigation systems. These results are entered into the spreadsheet. The spreadsheet is reviewed to see if the quantity of hazardous material triggers a PSM Rule site evaluation, if the release of materials would result in exposures that exceed exposure limits. If either or both of these are true for any chemical, a detailed PSA is in order. The next step is to prepare the spreadsheet information as a report that details the investigation, provides the data and the bases for recommending a detailed PSA. This report is sent to the responsible management for their action.

7,3.2 Performing a Detailed Probabilistic Safety Analysis

Step 1 Define CPQRA Goals.Objectives, Depth of Study, etc. ..__..._. _...^

Alan 9

i

Table 7.3.2-3 lists investigations to be conducted and documented for a detailed chemical plant PSA. The steps are similar to those required for a nuclear plant PSA except the hazards are more varied, and dispersed regarding concentration and location. Many of the steps previously described in Section 6.3.2 are applicable for the chemical PSA as well. Figure 7.3-2, from CCPS (1989) details the work and

\

Describe System r*" Step 3 Identify Hazards

Equipment Design, Chemistry, Thermodynamics, Operating Procedures, etc.

....

If f*

Experience, Codes, ChecMists, HAZOPS

t

Step 4 L Enumerate Incidents J

i Steps

I Select Incidents I

X "

Step 6 Consequence and Effect ~ Models, Decision Criteria " ~ "' Estimate Consequences T C»H» (Consequences Acceptably Low at any Frequency) too Hlf

Step? Modify System to Reduce Consequences V»o

*

Design Acceptable

Historical Analysis, Fault Tree Steps Analysis, Event Tree Analysis, > •& Estimate Frequencies Decision Criteria

*- (Frequences Acceptably Low for

any Consequence)

^f Fr«» utncies aTI ma High

4

Step 9

YfS

Frequencies

t*

Step 10 Decision Criteria [•--•> Combine Frequencies ano Consequences to Estimate Risk

-+

Design Acceptable (Combination of Consequences and Frequencies Acceptably Low)

y Kilkt art loa high 4

Y«

Step 11 Modify System to Reduce Risk

Lagand 3» of the type of particle in the type of material „ dN^~ ~N*dx/<x> (8.3-7) Tr -N/N =f»Yn(-y/ 3), Cd ~ 0.81. For cases where Cd is unknown or uncertain use €,, =1 to conservatively over-estimate the flow. Numerical Example: Hydrogen Release A container of hydrogen at 2 bar at 27 ° F is damaged causing a 1 cm2 sharp-edged opening. What is the rate of hydrogen discharge into the atmosphere? y for hydrogen is 1.43; for which equation 9.1 -19 gives rcri{ = 1.9. The velocity of sound is 1,888m/s, for sonic flow ij; = 0.828, and Cd = 1. Using these numbers in equation 9.1 -20, gives Q = 4.4E-3 kg/sec.

9.1.4 Liquid Discharge from a Hole in a Tank Liquid discharge from the work of Bernoulli and Torricelli is given by equation 9.1-23, where p is the liquid Q=Cd*A*p*S[2*(phj-ph)/p + 2*g*h] (9,1-23) density (kg/ni3), g is the acceleration of gravity (9.81 m/s2), and h is the liquid height above the hole (CCSP, 1989). The discharge coefficient for fully turbulent flow from sharp orifices is 0.61 -0,64. Numerical Example: Break in a Pressurized Tank holding Benzene A tank of benzene (specific gravity 0.88) pressurized to 2 bar (1 bar above atmospheric) is damaged causing a 10 cm2 sharp opening located 2 m below the liquid level. What is the discharge rate? Q = 0.64*(l/1000)*.88*1000*/(2* 1.013E5/880 + 2*9.81*2) = 9.24 kg/s. It may be noted that the gravity head only contributed about 10% of the effect of the internal pressure.

9.1.5 Unconfined Vapor Cloud Explosions (UVCE)a Explosions

Chemical explosions are uniform or propagating explosions. An explosion in a vessel tends to be a uniform explosion, while an explosion in a long pipe is a propagating explosion. Explosions are deflagrations or detonations. In a deflagration, the burn is relatively slow, for hydrocarbon air mixtures the deflagration velocity is of the order of 1 m/s. In contrast, a detonation flame shock front is followed closely by a combustion wave that releases energy to sustain the shock wave. A

The material in this section is adapted from Lees (1986) and CCPS (1989),

338

Hazardous Release

steady state detonation shock front travels at the velocity of sound in the hot products of combustion. For hydrocarbon-air mixtures the detonation velocity is typically of the order of 2,000 to 3,000 ro/sb, A detonation generates greater pressures and is more destructive than a deflagration. While the peak pressure caused by the deflagration of a hydrocarbon-air mixture in a closed vessel at atmospheric pressure is of the order of 8 bar, a detonation may have a peak pressure of the order of 20 bar. A deflagration may turn into a detonation if confined or obstructions to its passage. A basic distinction is made between confined unconfined explosions. Confined explosions occur within some sort of containment such as a vessel pipework, or a building. Explosions in the open air are unconfined explosions, If a large amount of a volatile flammable material is rapidly dispersed to the atmosphere, a vapor cloud forms. If this cloud is ignited before the cloud is diluted below its lower flammability limit, a UVCE occurs which can damage by overpressure or by thermal radiation.c"d Rarely are UVCEs detonations; it is believed that obstacles, turbulence, and possibly a critical cloud size are needed to transition from deflagration to detonation. Even if a flammable vapor cloud is formed, ignition is necessary for a UVCE. However, there are numerous ignition sources such as fired heaters, pilot flames smoking, vehicles, electrical equipment, etc. A site associated with many ignition sources tends to prevent a cloud from reaching its full hazard extent. *E vF= Conversely, at such a site, there is less likelihood for a cloud to (9,1-24) TNT disperse without ignition. A PSA should take account of the ignition probability. Early ignition, would result in a flash fire or an explosion of smaller size; late ignition could result in the maximum possible effect being experienced,

Model of UVCE UVCEs are modeled by equivalence of the flammable material to TNT by correlations with observed UVCEs (TNO model), or by computer modeling. Only the simple TNT model is discussed here. Equation 9.1-24 presents this model, where W is the equivalent weight of TNT, mc is the weight of material in the cloud, TJ is the empirical explosion yield (from 0.01 to 0.1) Ec is the heat of combustion of the cloud and Ej-NT is the heat of combustion of TNT (Table 9.1-4 for other units, 1 kJ/kg = 2,321 BTU/lb = 4.186 calories/gm). b

Table 9.1- 4 Some Heats of Combustion (from Baumeister, 1967) Name kJ/kg Name kJ/kg acetylene 5.0E4 hydrogen 1.4E4 butane 5.5E4 5.0E4 methane 5.2E4 methanol 23E4 ethane ethanol 3.0E4 octane 4.7E4 5.0E4 ethylene 5.0E4 propane 4.8E4 TNT hexane 4.7E3

The velocity of sound in air at 0° C is 330 m/s.

c

UVCEs were used in Vietnam, rather unsuccessfully, to send an overpressure into the underground tunnels. d

The Flixborough accident (Section 7.1.2.3) is an often-cited example of a UVCE. 339

Chemical Process Accident Consequence Analysis

Explosion Efficiency If the explosion occurs in an unconfmed vapor cloud, the energy in the blast wave is only a small fraction of the energy calculated as the product of the cloud mass and the heat of combustion of the cloud material. On this basis, explosion efficiencies are typically in the range of 1-10%. In some cases, however, only the part of the cloud which is within the flammable range is considered to burn. This may be a factor of 10 less than the total cloud. For further discussion of explosion efficiency see CCPS (1989) or Leeds (1986). Physical Parameters from the Explosion Explosion effects have been studied extensively. Figure 9.1-4 from Army (1969) uses 1/3 power scaling of the TNT equivalent yield obtained from equation 9.1-24. This graph is for a hemispherical blast such as would occur if the cloud were lying on the ground. To find the blast effects at a certain distance, calculate the scaled ground distance from the blast using: Zg = R/Wi/3, where Rg is the actual ground distance, Z g is the distance for scaling, and W is the equivalent TNT weight in pounds. Using a vertical line from this location on the abscissa, from the point of interception on a curve of interest go horizontally left or right according to the type of information and read the value. Calculating the Peak Positive Pressure from a Propane Explosion If 10 tons of propane exploded with an explosive efficiency 0.05, 1,000 ft from you, what would be the peak positive overpressure? Referring to equation 9.1-24, W = 0.05*2E4*5E4/4.7E3 = 1E4 Ib, where the heats of combustion are from Table 9.1-4, and 10 tons is 2E4 Ib. The scaled range is Zg = 1000/1E4"3 = 45.6 from which a positive overpressure of 2 340

Table 9.J-5 Damage Produced by Blast Overpressure

psi

Damage

0.02 Annoying noise (137 dB if of low frequency 10- 15 Hz) 0.03 Occasional breaking of large glass windows already under strain 0.04 Loud noise (143 dB), sonic boom glass failure 0.1

Breakage of small windows under strain

0.15 Typical pressure for glass breakage 0,3

"Safe distance" (probability 0.95 no serious damage beyond this value); projectile limit; some damage to house ceilings; 10% window glass broken

0.4

Limited minor structural damage

0.5- Large and small windows usually shattered; I occasional damage to window frames 0.7

Minor damage to house structures

1

Partial demolition of houses, made uninhabitable

1-2

Corrugated asbestos shattered; corrugated steel or aluminum panels, fastenings fail, followed by buckling; wood panels {standard housing) fastenings fail, panels blown in

1.3

Steel frame of clad building slightly distorted

2

Partial collapse of walls and roofs of houses

2-3

Concrete or cinder block walls, not reinforced, shattered

2.3

Lower limit of serious structural damage

2,5

50% destruction of brickwork of houses

3

Heavy machines (3,OOOIb) in industrial building suffered little damage; steel frame building distorted and pulledaway from foundations

3-4

Frameless, self-framing steel panel building demolished; rupture of oil storage tanks

4

Cladding of light industrial buildings ruptured

5

Wooden utility poles snapped; tall hydraulic press (40,000 Ib) in building slightly damaged

5-7

Nearly complete destruction of houses

7

Loaded train wagons overturned

7-8

Brick panels, 1 2 in. thick, not reinforced, fail by shearing or flexure

9 10

Loaded train boxcars completely demolished Probable total destruction of buildings; heavy machines tools (7000 Ib) moved and badly damaged, very heavy machine tools (12,000 Ib) survived

Hazardous Release

i/W"

i/w11 L,fW''

IJW" i/W"

1 Scaled Distance Z, =

o.i

i 10 Scaled Ground Distance Z, =

Fig. 9.1-4 Shock Wave Parameters for a Hemispherical TNT Surface Explosion at Sea level. Left ordinate: Psa - peak positive incident pressure, /*,,.„ - peak negative incident pressure, Pr - peak positive normal reflected pressure, P.r peak negative normal reflected pressure, i/w'/3 positive incident impulse, ijw'/3 - negative incident impulse, i/w'/} - positive normal reflected impulse, i,/wia - negative normal reflected impulse, iA/wi/3 - time of arrival, i,/w'/3 - positive duration of positive phase, i,,/wl/3 - negative duration of positive phase, Ln/w'a - wavelength of positive phase, L.Jwm - wavelength of negative phase. Pressure is in psi, scaled impulse is in psims/lbla, arrival time in ms/lb"3, wavelength is in ft/lbl/}, RK is the scaled ground distance from the charge. W is the charge weight in Ib.

341

Fig. 9.1-5 Shock Wave Parameters for a Spherical TNT Surface Explosion at Sea level. Left ordinate: Pm - peak positive incident pressure, P.w - peak negative incident pressure. Pr - peak positive normal reflected pressure P, peak negative normal reflected pressure, i/w''J positive incident impulse, i,/wl/J - negative incident impulse, i/w"1 - positive normal reflected impulse, i./w"3 - negative normal reflected impulse, iA/w'/3 - time of arrival, ?,/»''" positive duration of positive phase, Z,/H'"* negative duration of positive phase, LM/wl/J wavelength of positive phase. L_K/w!''! wavelength of negative phase. Pressure is in psi, scaled impulse is in psi-ms/lb'a, arrival time in ms/lb/a, wavelength is inft/lb1", R. is the scaled distance from the charge. W is the charge weight in Ib.


psi. is read, Table 9. 1-5 indicates that this will cause partial collapse of walls and roofs of houses, concrete or cinder block walls, not reinforced, shattered, lower limit of serious structural damage.

9.1,6 Vessel Rupture (Physical Explosion)6 If a vessel containing a pressurized gas or vapor raptures, the release of the stored energy of compression produces a shock wave and flying vessel fragments (CCSP, 1989). Previously we modeled explosive reaction of the gas with air if such energy also is involved, the effects will be more severe. Such vessel ruptures may occur from: 1) over-pressurization of the vessel which involves failure of the pressure regulators, relief valves and operator error, and 2) weakness of the pressure vessel from corrosion, stress corrosion cracking, erosion, chemical attack, overheating material defects, cyclic fatigue or mechanical damage. The energy that is released is in the form of: i) kinetic energy of fragments, 2) energy in shock wave, 3) heat (e.g., the surrounding air), and 4) the energy of deformation. Estimates of how the energy is distributed are 40% goes into shock wave energy with the remainder in fragment kinetic energy if the vessel brittle fractures. In general the explosion is not isotropic but depends on the tank geometry and crack propagation. If the tank is filled with gas, the energy comes from the compression of the gas into the full volume; if the tank contains a liquid with vapor space, it is the energy of compression in the vapor space; if the tank contains a superheated liquid, the energy comes from flash evaporation. Empirical Model It is convenient to calculate a TNT equivalent of a physical explosion to use the military results of Figures 9.1-4 and 5. Baker et al. (1983) give a recipe for the rupture of a gas filled container assuming expansion occurs isothermally and the WÂE^V^P./P perfect gas laws apply (equation 9.1-25), where W is the energy in TNT Ib equivalence, V is the volume of the compressed gas (ft3), P is the initial pressure of the compressed gas (psia), P2 is the pressure of expanded gas (psia), P0 is sea level pressure (14.7 psia), T, is the temperature of compressed gas (°R), T0 is standard temperature (492° R), R is the gas constant (1.987 Btu /lb-mol-°R, and 1 .4E-6 is a conversion factor assuming 2,000 Btu per 1 Ib of TNT. This calculates TNT equivalence to estimate shock wave effects, but it is not valid in the near field. The blast pressure, Ps, at the surface of an exploding pressure vessel is estimated by Prugh (1988) with equation 9.1-26 where Ps is the pressure at surface of vessel (bara), Pb is the burst (9.1-26)

Adapted from CCSP, 1989.

342

Hazardous Release

pressure of vessel (bara), y is the ratio of specific heats, (Cp/Cv), T is the absolute temperature, (°K), and M is the molecular weight of gas, (Ib/lb mole). This assumes that expansion occurs into air at STP. Notice equation 9. 1 -25 does not directly give what we want, the pressure at the surface of the bursting vessel. Instead of an analytic inversion, Program 9-1 iterates to find Ps given Pb. After finding Ps, and the scaled distance, Z, the explosion parameters are found from Figure 9, 1 -4.

1 2 3 4 5 6 7 8 9 10

Program 9-1 Calculating the Surface Pressure CLS : INPUT "Burst pressure (bara)", pb gamma = 1.4: temp = 300 INPUT "Molecular weight of gas (Ib/lb-mole) ", mole DO ps = ps +0. 1 pbc = ps * (1 - (3.5 * (gamma - 1) * (ps - 1)) / ((gamma * temp / mole) * (1 + 5,9 * ps)) A ,5) A (-2 * gamma/ (gamma - 1)) LOOP UNTIL pbc > pb PRINT "Surface pressure (bara) "; ps

Line 1 clears the screen and requests the input of the burst pressure of the vessel. Line 2 sets gamma to 1.4 and the absolute temperature to 300. If your pressure or temperature is different, edit the program Line 3 requests the molecular weight of the gas in the vessel. Lines 5-10 loop to perform the iteration. Line 6 iterates the surface pressure in steps of 0.1 bara. Lines 7-9 are equation 9.1-25. Line 10 stops the iteration when pbopb, and line 1 1 prints ps.

Example: Pressures from a Bursting Tank A 6 ft3 compressed air spherical tank at 15° C bursts at 546 bara. What is the side-on over pressure at 25 and 50 ft? From equation W = 1.4E-6*V*(P,/P0)*( T0/T,)*R*T1*ln(P(/P2), = 1.4E6*6*(7917/14.7)*(492/518)*1.987*518*ln(7917/14.7) = 27.8 Ib TNT. By running program 9-1, using Pb = 546 bara and M = 28.9 we find 10.3 bara = 149.3 psia. From Figure 9.1-4, we read Zg = 3. 1 for this pressure. Using the TNT equivalence, we find Rg 9.4 ft. For V = 6 = 4/3*ir*r3, r = 1 . 13 ft. Rg corrected to the center of the sphere is 9.4-1. 1 = 8.3 ft. The blast pressure at 254-8.3 = 33,3 ft. has a Zg = 33.3/27.8!/3 = 1 1.0 at which Figure 9.4-1 gives Pr = 8 psig. At 50 ft., Zg = 58.3/27.8'* -- 19.2 and the figure shows Pr = 3.1 psig.

9.1,7 BLEVE, Fireball and Explosion* A boiling liquid expanding vapor explosion (BLEVE) may result from a fire that impinges on the vapor space of a tank of flammable liquid to weaken the tank material and build vapor pressure to such an extent that the tank ruptures and the superheated liquid flashes to vapor and explodes generating a pressure wave and fragments (CCSP, 1989). BLEVEs while rare, are best known for involving liquefied petroleum gas (LPG). The vessel usually fails within 10 to 20 minutes from the time of impingement. Incidents occurred at: San Carlos, Spain (July 11, 1978), Crescent City, Illinois (June 21, 1970), and Mexico City, Mexico (November 19, 1984). The fireball modeling is separate from the projectile modeling.


343


BLEVE Fireball Physical Parameters

Useful formulas for BLEVE fireballs (CCSP, 1989) are given by equations 9.1-27 thru Diameter(m) £>max = 6.48M0325 flammable Durations) t = 0.825Ma2ft 9,1-30, where M = initial mass of liquid (kg). The initial diameter describes the short Height(m) H=Q.75D duration initial ground level hemispherical HemldiaAm) D HHta« .. , = 1.3*lT ,. , i _r i - & -j. . max tlaming-volume before buoyancy ihits it to an equilibrium height.

(9.1 -27) (9.1-28) (9 1-29) /o i *m V"- l~JV)

Thermal Radiation from the Fireball

The thermal radiation received from the fireball on a target is given by equation 9.1-31, where Q is the radiation received O = t *£ * F (9131) by a black body target (kW/m2) r is the atmospheric transmissivity (dimensionless), E- surface emitted flux in t=2.02*(p *;c)~a09 (91-32) 2 kW/m , and F is a dimensionless view factor. The atmospheric transmissivity, T, greatly affects the / *M*h radiation transmission by absorption and scattering by the E= (9.1-33) n separating atmosphere. Absorption may be as high as *^m^t 20-40%. Pietersen and Huerta (1985) give a correlation that /) 2 accounts for humidity (equation 9.1-31), where T = ? (9.1-34) A . . . . . • , 4*1"" atmospheric transmissivity, pw = water partial pressure (Pascals), x = distance from flame surface to target (m). The heat flux, E, from BLEVEs is in the range 200 to 350 kW/m2 is much higher than in pool fires because the flame is not smoky. Roberts (1981) and Hymes (1983) estimate the surface heat flux as the radiative fraction of the total heat of combustion according to equation 9.1-32, where E is the surface emitted flux (kW/m2), M is the mass of LPG in the BLEVE (kg) hc is the heat of combustion (kJ/kg), Dmax is the maximum fireball diameter (m) frad is the radiation fraction, (typically 0.25-0.4). t is the fireball duration (s). The view factor is approximated by equation 9.1-34, where D is the fireball diameter (m), and x is the distance from the sphere center to the target (m). At this point the radiation flux may be calculated (equation 9.1-30). Problem: Size Duration and Flux from a BLEVE (CCSP, 1989)

Calculate the size duration, and flux at 200 m from 100,000 kg (200 m3) tank of propane at 20° C, 8.2 bara (68° F, 120 psia). The atmospheric humidity has a water partial pressure of 2,710 N/m2 (0.4 psi). BLEVE parameters are calculated from equations 9.1-26 to 9.1-29: Dmax = 6.48* 1E5°'32S = 273 m. H = 0.75*273 = 204 m. Dinitiai = 1.3*273 = 354 m. Using a radiation fraction frad = 0.25, the view factor from equation 9.1-33 is: F = 2732/(4*200)2 = 0.47. The path length for the transmissivity is the hypotenuse of the elevation and the ground distance minus the BLEVE radius: /(2042+2002) - 273/2 = 150 m. The transmissivity from equation 9.1-31 is: t = 2.02*(2820*150)'009 = 0.63. The surface emitted flux from equation 9. L-32 is: 0.25* !E5*46,350/(Tt*2732* 16.5) = 300 kW/m2, and the received flux from equation 9.1 -30 is 0.63*300*0.47 = 89 kW/m2. 344

Hazardous Release 9

9.1.8 Missiles

Number of Missiles The explosion from an explosion generates heat, pressure and missiles. Studies have been performed by: Baker (1983), Holden and Reeves (1985) and the Association of American Railroads, AAR (1972) AAR (1973), AAR reports out of 113 major failures of tank cars in fires, about 80% projected fragments. The projections are not isotropic but tend to concentrate along the axis of the tank. 80% of the fragments fall within a 300-m range (Figure 9.1-6). Interestingly, BLEVEs from smaller LPG vessels have greater range, The total number of fragments is a function of vessel size and perhaps other parameters. Holden (1985) gives a correlation based on 7 incidents as equation 9.1-35, where F is the number of fragments and V is the vessel volume in m3 for the range 700 to 2,500 m3.

* 4I

? f * *

PBTcant Fragments wifri Range < H (m,

Fig. 9.1-6 Range of LPG Missiles (Holden, 1985)

F= -3.77 +0.0096*¥ (9.1-35) Example: Explosion of a Propane Tank (CCSP, 1989) Fire engulfs a 50 ft-dia. propane tank filled to 60% capacity. The tank fails at 350 psig. Estimate the energy release, number of fragments, and maximum range of the missiles. The volume of the tank is: V = it*D3/6 = 6.5E4 ft3. The volume of the liquid is 6.5E4 * 0.6 = 3.9E4 ft3 and vapor occupies 6.5E4 * 0.4 = 2.6E4 ft which is considered to cause the explosion. Equation 9.1-25 estimates W = 2.8E3 Ib TNT (using Tl = 614). The number of fragments may be estimated from equation 9.1-35 using the vapor space (2.6E4/35.28 = 737 m3) to be F = 4 (rounding up). The surface area of the spherical shell is A = 7t*D2 = 7854 ft2, and the volume is 490.8 ft1 (for a thickness t = 0.75 in.). The weight of the shell is 490.8*489 lb/ft3 = 2.4E5 Ib so the average fragment weight is 6E4 Ib. The area of a fragment is 7854/4 = 1,964 ft2 which, if circular, the diameter is 50 ft. = 600 in. The velocity of a fragment is estimated from Moore u=2.05*(P*D3/W)m (9.1-36) (1967) equation 9.1-36, where u is the initial velocity in ft/s, P is the rupture pressure psig, D is the fragment diameter in inches, and W is the weight of fragments in Ib. Substituting into equation 9.1-36 gives the fragment initial speed as 2,300 ft/s.


345


The next step is to estimate the lift/drag ratio 1°| _ .° for a fragment: CL*AL/CD*AD. For a "chunky" ! - ' " 1 fragment C,*AL/CD*AD = 0. The drag coefficient, , v CD, ranges from 0.47 to 2.05 for a long rectangular fragment perpendicular to the air flow. Take CD = "'•' ,0 0.5 for this case and use Figure 9.1-7 °* /, 30 30 to estimate the range. The axes are scaled by B = pa " *Cd*Ad IM where pa is the density of air (0.0804 M| "° §& lbra/ft3), Cd is the drag coefficient, Ad is the area of a | fragment, ft2, M is mass in Ibm. The ordinate is B*R, L--^ —^j- - - J-^— .j . w where /? is maximum fragment range, ft. The Fig. , - cScaled , . *,Fragment"V,Range vsc.Scaled , , r.Force & & r. n9.1-7 abscissa is B*ir/g where M is fragment velocity ft/s, ^>.om ga£er er a/., 7953 and g is the acceleration of gravity, 32.2 ft/sec2. For this case, B = 0.0804*0.5*1964/6E4 = 1.32E-3. The abscissa is B*5.29E6/32.2 = 217. The corresponding ordinate for the "0" curve is 5.5 = B*R giving R = 4166 ft.

9.2 Chemical Accident Consequence Codes The chemical and physical phenomena involved in chemical process accidents is very complex. The preceding provides the elements of some of the simpler analytic methods, but a PSA analyst should only have to know general principles and use the work of experts contained in computer codes. There are four types of phenomenology of concern: 1) release of dispersible toxic material, 2) dispersion of the material, 3) fires, and 4) explosions. A general reference to such codes is not in the open literature, although some codes are mentioned in CCPS (1989) they are not generally available to the public. However, around 1995, U.S. DOE through its Defense Programs (DP), Office of Engineering and Operations-Support, established the Accident Phenomenology and Consequence (APAC) Methodology Evaluation Program to identify and evaluate methodologies and computer codes to support accident phenomenological and consequence calculations for both radiological and nonradiological materials at DOE facilities and to identify development needs. APAC is charged to identify and assess the adequacy of models or computer codes to support calculations for accident phenomenology and consequences, both inside and outside the facility, associated with chemical and/or radiological spills, explosions, and fires; specify dose or toxic reference levels for determining off-site and on-site radiological/toxicological exposures and health effects. Six working groups were formed of these, the reports of four are used: 1) the Spills Working Group, Brereton 1997; 2) the Chemical Dispersion and Consequence Assessment Working Group, Lazaro, 1997; the Fire Working Group, Restrepo, 1996; and 4) the Explosions and Energetic Events Working Group, Melhem, 1997. In addition to this, material that I found on the Internet is presented as well as material that was requested via the Internet.

346

Chemical Accident Consequence Codes

9.2.1 Source Term and Dispersion Codes

Some codes just calculate source terms (release quantities) and others just calculate the dispersion after release, and some codes do both. Each heading in the following identifies the code's capability, 9.2.1.1 Adam 2.1 (Release and Dispersion) The Air Force Dispersion Assessment Model (ADAM -1980s) calculates the source term and dispersion of accidental releases of eight specific chemicals: chlorine, fluorine, nitrogen tetroxide, hydrogen sulfide, hydrogen fluoride, sulfur dioxide, phosgene, and ammonia. It treats a wide spectrum of source emission conditions (e.g., pressurized tank ruptures, liquid spills, liquid/vapor /two-phase) and a variety of dispersion conditions (e.g., ground-based jets or ground-level area sources, relative cloud densities, chemical reactions and phase changes, and dense gas slumping) including reactions of the chemical with water vapor. It has been validated using a number of field experiment data. The pool evaporation model is Ille and Springer (1978) for non-cryogenic spill and Raj (1981) for cryogenic spills. Liquid release from a tank uses Bernoulli's equation but does not account for pressure variation or level drop. Gas release from a tank uses 1-d compressible flow equations for the release rate and temperature, pressure variation or level drop is not treated. Adiabatic flashing and rainout are not included. The turbulent jet model is Raj and Morris (1987). ADAM would require source code modification to include any but its 8 chemicals.. It assumes that the jet is ground-based and horizontally-directed; the vertical component of the jet trajectory in the transport and dispersion calculations is not included; it does not treat rainout and assumes all droplets remain airborne until evaporated, Output: mass rate and vapor temperature of release, mass rate of air entrained, density of mixture, aerosol mass fraction in cloud. Limitations: single chemical source terms, limited chemical database, only steady-state release, based on spill data of rocket propellants. Sponsor/Developer: AL/EQS, Tyndall AFB, FL. Developer: TMS, Burlington, MA. Custodian: Captain Michael Jones, AL/EQS, 139 Barnes Drive, Tyndall AFB, FL 32403-5319, Phone: (904) 283-6002 Developer: Dr. Phani Raj, TMS Inc., 99 South Bedford St., Suite 211, Burlington, MA 01803-5128 Phone: (617) 272-3033. Cost: None. The source and executable versions of the code may be downloaded from EPA's web site: http://www.epa.gov/scram001/t22.htm. Look in "Non-EPA Models (277kB ZIP). Computer: IBM compatible, math co-processor recommended, 512 kB RAM, runs in DOS, menu driven. 9.2.1.2 AFTOX (Version 3.1 Dispersion) AFTOX is a Gaussian dispersion model that is used by the Air Force to calculate toxic corridors in case of accidental releases. Limited to non-dense gases, it calculates the evaporation rate from liquid spills. It treats instantaneous or continuous releases from any elevation, calculates buoyant plume and is consistent with ADAM for passive (neutrally-buoyant) gas releases.

347


Dispersion calculations use standard Gaussian formulas. Stability class is treated as a continuous variable with averaging time. Output: Maps of toxic corridors, estimates of concentration at specific positions, and estimates of the magnitude and location of the maximum concentration occurring a certain time after release. Sponsor/Developing Organization: Phillips Laboratory Directorate of Geophysics, Air Force Systems Command, Hanscom AFB, MA 01731-5000. Custodian: Steven Sambol, 30 WS/WES, Vandenberg AFB, CA 93437-5000, Phone: (805) 734-8232. Cost: None, May be downloaded from EPA's website: http://www.epa.gov/scram001/t22.htm. Look in "Non-EPA Models" for files AFTOX Toxic Chemical Dispersion Model (173 kB ZIP), and AFTOXDOC AFTOX Model User's Guide, ASCII (26 kB ZIP) 9.2.1.3 Area! Locations of Hazardous Atmospheres (ALOHA) 5.2 - Release and Dispersion) ALOHA is an emergency response model for rapid deployment by responders, and for emergency preplanning. It computes time-dependent source strength for evaporating liquid pools (boiling or non-boiling), pressurized or nonpressurized gas, liquid or two-phase release from a storage vessel, and pressurized gas from a pipeline. It calculates puff and continuous releases for dense and neutral density source terms. Model output is provided in both text and graphic form and includes a "footprint" plot of the area downwind of a release, where concentrations may exceed a user-set threshold level. It accepts weather data transmitted from portable monitoring stations and plots footprints on electronic maps displayed in a companion mapping application, MARPLOT. The modified time-dependent Gaussian equation is based on Handbook on Atmospheric Diffusion and the heavy gas dispersion is based on Development of an Atmospheric Dispersion Model for Heavier-Than Air Gas Mixtures. The dense gas submodel of ALOHA is a simplified version of the DEnse GAs DISpersion (DEGADIS) model. It calculates pool evaporation using conservation of mass and energy; an analytical solution of the steady-state advection-diffusion equation calculates the evaporation mass transfer from the pool (Brighton, 1985). The liquid release from a tank is calculated with the Bernoulli equation. Leaked material is treated with the pool evaporation model, puddle growth is modeled (Briscoe and Shaw, 1980). It treats heat conduction from the tank and evaporative heat transfer into the tank vapor. Gas release rate and temperature from a tank is calculated using one-dimensional compressible flow equations. A virial equation of state handles high pressure non-ideal gas behavior. (Belore and Buist, 1986; Shapiro, 1953; Blevins; 1985, and Hanna and Strmiaitis, 1989). Two-phase tank release assumes quick evaporation, thus, no liquid pool is formed. Releases through a hole are modeled with Bernoulli's equation modified for the head and pressure of the liquid gas mixture. Release though a short pipe is modeled with a homogenous non-equilibrium model while release through a long pipe uses a homogenous equilibrium model (Fauske and Epstein, 1988; Henry and Fauske, 1971; Leung, 1986; Huff, 1985; and Fisher, 1989). ALOHA has a comprehensive chemical source term library (>700 pure chemicals). The code can address many types of pipe and tank releases, including two-phased flows from pressurized/ cryogenic chemicals. The user may enter a constant or variable vapor source rate and duration of 348


release. Vertical wind shear is included in the pool evaporation model as well as the Gaussian (passive) and heavy gas dispersion models. ALOHA only models the source-term and dispersion of single-component, nonreactive chemicals. It does not account for terrain steering or changes in wind speed and horizontal direction. It does not model aerosol dispersion, nor does it account for initial positive buoyancy of a gas escaping from a heated source. Its straight-line Gaussian model prevents addressing scenarios in complex terrain. Sponsors! National Oceanic and Atmospheric Administration, Hazardous Materials Response and Assessment Division, 7600 Sand Point Way N.E. Seattle, WA 98115; United States Environmental Protection Agency Chemical Emergency Preparedness and Prevention Office,Washington, D.C. 20460, National Safety Council. Custodians: Dr. Jerry Gait, NOAA/HAZMAT, 7600 Sand Point Way N.E., Seattle, WA 98115, Phone: (206) 526-6323, E-mail: jerry [email protected]. Mark Miller Phone: (206) 526-6945, E-mail: [email protected]. Cost: -$375. Computer: IBM compatible, 386 with math coprocessor desired, Windows 3.0 or higher, 1 MB RAM, 2.5 MB hard drive, or Macintosh. 1 MB RAM and 2 MB hard drive runs under Finder or Multifinder. 9.2.1.4 CALPUFF (Dispersion) CALPUFF is a multilayer, multispecies non-steady-state puff dispersion model that simulates the effects of time- and space-varying meteorological conditions on chemical transport, transformation, and removal. It uses 3-dimensional meteorological fields computed by the CALMET preprocessor or simple, single-station winds in a format consistent with the meteorological files used to drive the ISC3 or AUSPLUME steady-state Gaussian models. CALPUFF contains algorithms for near-source effects such as building downwash, transitional plume rise, partial plume penetration, sub-grid-scale complex terrain interactions and longer range effects such as pollutant removal (wet scavenging and dry deposition) chemical transformation, vertical wind shear, and overwater transport. It has mesoscale capabilities that are not needed for chemical spill analysis. Most of the algorithms contain options to treat the physical processes at different, levels of detail, depending on the model application. Time-dependent source and emission data from point, line volume, and area sources can be used. Multiple option are provided for defining dispersion coefficients. Time-varying heat flux and emission from fire can be calculated with the interface to the Emissions Production Model. A graphical users interface includes point and click model setup and data entry, enhanced error checking of model inputs and online help files, Although CALPUFF is comprehensive, it was not designed for simulating dense gas dispersion effects or for use in evaluating instantaneous or short-duration releases of hazardous materials. The model is best applied to continuous releases rather than short-duration releases from accidents. Averaging times are long (minimum of one hour) for input data (release rate and meteorology) and output. Terrain effects on vapor dispersion may be modeled in the code. However, dispersion of heavier-than-air releases is not considered. It does not have a built in library of chemicals or a spills front end. Version 6 has provisions for time steps of less than one hour. The easy interface, documentation, detailed final results and intermediate submodel output comprise a useful code. 349


Sponsor: U.S. Environmental Protection Agency, U.S. Department of Agriculture, Forest Service, California Air Resources Board, and several industry and government agencies in Australia, Developer: Earth Tech (formerly Sigma Research). Custodian: John Irvin, U.S. Environmental Protection Agency. Cost:. None. May be downloaded from EPA's Website; http://www.epa. gov/scram001/t26.htm. Look under CALPUFF for files READ1ST 8/01/96 CALPUFF MUST READ FIRST (12kB TXT), CALPUFFA 7/11/96 CALPUFF Modeling System-File A (1,146K.ZIP), CALPUFFB 7/11/96 CALPUFF Modeling System-File B (456K,ZIP), CALPUFFC 7/11/96 CALPUFF Modeling System-File C (l,040kB ZIP), CALPUFFD 7/11/96 CALPUFF Modeling System-File D (1,082 k.B ZIP). 9.2,1.5 CASRAM/Beta 0.8 (Release and Dispersion) CASRAM calculates the source emission rate for accidental releases of chemicals, as well as the transport and dispersion of these chemicals in the atmosphere. The evaporation of liquid pools of spilled chemicals is treated in great detail; however, no algorithms are included for the emission rate from pressurized jet releases. The specifications of atmospheric boundary layer parameters and the vertical dispersion of plumes are modeled with state-of-the-art methods. CASRAM does not treat dense gas releases, and it is assumed that the height of the release is near the ground. The Monte Carlo version allows for variability in key parameters pertaining to accident location, time and spill characteristics. Output parameters include the maximum concentration and plume width as a function of downwind distance. Two versions of the model exist: 1) the main CASRAM calculates mean, variance and other statistics of model predictions, thus, accounting for known variabilities; and 2) the deterministic version (CASRAM-CD) calculates only the mean. CASRAM's technical documentation and code are in draft (Brown et al.,1977a, 1977b, 1994a, 1994b). The model contains a surface energy method for parameterizing winds and turbulence near the ground. Its chemical database library has physical properties (seven types, three temperature dependent) for 190 chemical compounds obtained from the DIPPRh database. Physical property data for any of the over 900 chemicals in DIPPR can be incorporated into the model, as needed. The model computes hazard zones and related health consequences. An option is provided to account for the accident frequency and chemical release probability from transportation of hazardous material containers. When coupled with preprocessed historical meteorology and population densities, it provides quantitative risk estimates. The model is not capable of simulating dense-gas behavior.

h

The DIPPR file contains textual information and pure component numeric physical property data for chemicals. The data are compiled and evaluated by a project of the Design Institute for Physical Property Data (DIPPR) of the American Institute of Chemical Engineers (AIChE). The numeric data in the DIPPR File consist of both single value property constants and temperature-dependent properties. Regression equations and coefficients for temperaturedependent properties are also given for calculating additional property values. All of the data are searchable, including regression coefficients, percent error, and minimum/maximum temperature values. 350


It can simulate a wide variety of release scenarios but is particularly well suited to assessing health consequence impacts and risk. CASRAM predicts discharge fractions, flash-entrainment quantities, and liquid pool evaporation rates used as input to the model's dispersion algorithm to estimate chemical hazard population exposure zones. The output of CASRAM is a deterministic estimate of the hazard zone (to estimate an associated population health risk value) or the probability distributions of hazard-zones (which is used to estimate an associated distribution population health risk). The release of a liquid from an unpressurized container or the liquid fraction from a pressurized release is assumed to be instantaneously spilled on the ground (e.g., Bernoulli's equation is not employed) thus, overestimating the initial liquid pool evaporation rate. Currently, CASRAM-SC models near-surface material concentrations from near-surface releases. Spills of multiple chemicals are treated in CASRAM-SC. In these instances, no interaction between chemicals is considered, but the combined toxicological effects are modeled as outlined in the American Congress of Government and Industrial Hygienists Threshold Limit Value (ACGffl-TLV) documentation. For stochastic simulations, accident times (year, day of year and hour) and spill fractions are determined by sampling distributions obtained from the HMIRS database. Relative spill coverage areas are sampled from a heuristic distribution formulated using average chemical property and pavement surface data. Sponsor: Argonne National Lab, Environmental Assessment Division, Atmospheric Science Section, 9700 S, Cass Ave., Argonne, IL 60439. Developer: University of Illinois, Dept. of Mechanical Engineering, 1206 W. Green, Urbana, IL 61801. Custodians: D.F. Brown University of Illinois, Dept, of Mechanical Engineering, 1206 W. Green, Urbana, EL 61801. Computer: It runs on a 486, Pentium PC, or any workstation. The deterministic version runs (slowly) on a 386. The stochastic version of the code was originally written for a Sun Workstation. The PC version requires at least a 486, 33 MHz machine with a minimum of 10 MB of free hard disk space. Cost: None?.

9.2.1.6 DEGADIS (Dispersion) DEGADIS (Dense GAs Dispersion) models atmospheric dispersion from ground-level, area sources heavier-man air or neutrally buoyant vapor releases with negligible momentum or as a jet from pressure relief into the atmosphere with flat unobstructed terrain. It simulates continuous, instantaneous or finite-duration, time-invariant gas and aerosol releases, dispersion with gravitydriven flow contaminant entrainment into the atmosphere and downwind travel. It accounts for reflection of the plume at the ground, and has options for isothermal or adiabatic heat transfer between the vapor cloud and the air. Variable concentration averaging times may be used and time-varying source-term release rate and temperature profiles may be used. It has been validated with large-scale field data. It models induced ground turbulence from surface roughness. The jet-plume model only simulates vertical jets. Terrain is assumed to be flat and unobstructed. Application is limited to surface roughness mush less than the dispersing layer. User expertise is required to ensure that the selected runtime options are self-consistent and actually reflect the physical release conditions. Documentation needs improvement; there is little guidance

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for effectively varying numerical convergence criteria and other program configuration parameters to obtain the final results. Sponsors: U.S. Coast Guard and the Gas Research Institute. Reference: Spicer, T. and J. Havens, 1989. Cost: Free. The source and executable versions of the code may be downloaded from EPA's website: http://www.epa.gov/scram001/t22.htm. Look in "other models." DEGATEC 1.1 DEGATEC is a user-friendly program that calculates the hazard zone surrounding releases of heavier than-air flammable and toxic gases. It incorporates the FORTRAN program DEGADIS 2.1, (Havens, 1985). Its Windows implementation inputs and outputs easier than the original DEGADIS2.1. DEGATEC was developed for the Gas Research Institute (GRI) by Tecsa Ricerca and Innovazione, s.r.l. (TRI) and Risk and Industrial Safety Consultants, Inc. (RISC). Custodian and Developer: Tecsa, Via Oratorio, 7, 20016 Pero (Ml), Italy, and Risk and Industrial Safety Consultants Inc., 292 Howard Street, Des Plaines, IL 60018, Hardware: 386 or better CPU with a math coprocessor. Calculations require about 2 MB hard drive and 4 MB of RAM. The resident file requires 3 MB of storage in the hard drive. Software:Windows 3.0 or higher. C&st: $900 for User's Manual, the executable program, protection key, quarterly bulletin, and telephone and fax support. GRAPHMAP, software that allows superimposition of DEGATEC concentration contours over a map, is available for an additional $200. 9.2.1.7 EMGRESP (Release and Dispersion) EMGRESP is a source-term and dispersion emergency response screening tool for calculating downwind contours with a minimum of user input and computational expense in the event of a release of a hazardous chemical. The program provides hazardous contaminant information, calculates toxic concentrations at various distances downwind of a release, and displays the information on the screen compared to threshold exposure levels such as the Threshold Limit Values (TLV), Short Term Exposure Limits (STEL), and Immediately Dangerous to Life and Health (IDLH), For a combustible release, the code gives an estimate of the mass of vapor within the flammable limits. Model Description References: Model description and references are provided in the user's manual (Diamond et al, 1988). References for EMGRESP are: Chong (1980); Eidsvik (1980); Fryer and Kaiser (1979); and Opschoor (1978). The source-term models consist of: gas release from a reservoir, a liquid release from a vessel, and liquid pool evaporation. The dispersion models are: neutrally buoyant Gaussian plume, instantaneous puff model, and an instantaneous dense gas "box" model. It has a large database of physical/chemical properties; the mass of vapor calculations within flammable concentration limits was confirmed with large-scale field data. EMGRESP is overly conservative for passive gas dispersion applications. No time-varying releases may be modeled. Dense gas dispersion may be computed for only "instantaneous" releases conditions. Sponsor/Developing Organization: Ontario Ministry of the Environment Air Resources Branch, 880 Bay St., 4th Floor, Toronto, Ontario M5S 1Z8, Phone: (416) 3254000. Website is:


http://www. cciw, ca/glinw/agency-search/other/omee.html. Custodians: Dr. Robert Bloxam, Science & Technology Branch, 2 St. Clair Ave. W., Floor 12A, Toronto, Ontario M4V 1L5, Phone: (416) 323-5073, Sunny Wong Science & Technology Branch 2 St. Clair Ave. W. Floor 12A Toronto, Ontario M4V 1L5 Phone: (416)323-5073. Computer: IBM PC compatible computer (8086 processor or greater), CGA or greater graphics support, 640 kB of RAM, DOS 3.0 or higher with GWBASIC. Corf: None. 9.2.1.8 FEM3C (Dispersion) FEM3C is a three-dimensional finite element model for simulation of atmospheric dispersion of denser-than-air vapor and liquid releases. It is useful for modeling vapor dispersion in the presence of complex terrain and obstacles to flow from releases of instantaneous or constant-rate vapors or vapor/liquid mixtures. The algorithm solves the 3-dimensional, time-dependent conservation equations of mass, momentum, energy, and chemical species. Two-dimensional calculations may be performed, where appropriate, to reduce computational time. It models isothermal and non-isothermal dense gas releases and neutrally buoyant vapors, multiple simultaneous sources of instantaneous, continuous, and finite-duration releases. It contains a theraiodynamic equilibrium submodel linked with a temperature-dependent chemical library for analyzing dispersion scenarios involving phase change between liquid and vapor state. It models the effects of complex terrain and obstructions to flow on the vapor concentration field using a number of alternate turbulence models. The user can model turbulence parameterized via the K-theory or solving the k-e transport equations. The code cannot accept typical vapor/aerosol source terms (e.g., pressurized jets, time-varying vapor emissions). Although the code treats complex terrain, modeling diverse vegetation in the same computation is difficult. The aerosol model does not model all relevant physical behavior (e.g., droplet evaporation and rainout). FEM3C is configured specifically for the Cray-2 (a parallel-processing computer), and, therefore, porting the code to another computing architecture would be a big job. Significant postprocessing of the output by the user is required to obtain concentration values at specific locations and averaging times. Sponsor: U.S. Army Chemical Research, Development and Engineering Center (CRDEC). Developer: Stevens T. Chan Lawrence Livermore National Laboratory, P.O. Box 808, Livermore, CA 94551-9900, Phone: (501) 422-1822 Custodian: Diana L. West, L-795 Technology Transfer Initiative Program, Lawrence Livermore National Laboratory Livermore, CA 94551, Phone: (510) 423-8030, 9.2.1.9 FIRAC (Release) FIRAC is a computer code designed to estimate radioactive and chemical source-terms associated with a fire and predict fire-induced flows and thermal and material transport within facilities, especially transport through a ventilation system. It includes a fire compartment module based on the FIRIN computer code, which calculates fuel mass loss rates and energy generation rates within the fire compartment. A second fire module, FIRAC2, based on the CFAST computer code, is in the code to model fire growth and smoke transport in multicompartment structures. 353


It is user friendly and possesses a graphical user interface for developing the flow paths, ventilation system, and initial conditions. The FIRIN and CFAST modules can be bypassed and temperature, pressure, gas, release energy, mass functions of time specified. FIRAC is applicable to any facility (i.e., buildings, tanks, multiple rooms, etc.) with and without ventilation systems. It is applicable to rnulti species gas mixing or transport problems, as well as aerosol transport problems. FIRAC includes source term models for fires and limitless flow paths, except the FIRIN fire compartment limit of to no more than three The PC version runs comparatively slow on large problems. FIRAC can perform lumped parameter/control volume-type analysis but is limited in detailed multidimensional modeling of a room or gas dome space. Diffusion and turbulence within a control volume is not modeled. Multi-gas species are not included in the equations of state. 9.2.1.10 GASFLOW 2.0 (Dispersion) GASFLOW models geometrically complex containments, buildings, and ventilation systems with multiple compartments and internal structures. It calculates gas and aerosol behavior of low-speed buoyancy driven flows, diffusion-dominated flows, and turbulent flows during deflagrations. It models condensation in the bulk fluid regions; heat transfer to wall and internal structures by convection, radiation, and condensation; chemical kinetics of combustion of hydrogen or hydrocarbons; fluid turbulence; and the transport, deposition, and entrainment of discrete particles, The level of detail GASFLOW is changed by the number of nodes, number of aerosol particle size classes, and the models selected. It is applicable to any facility regardless of ventilation systems, It models selected rooms in detail while treating other rooms in less detail. It calculates one-dimensional heat conduction through walls and structure; no solid or liquid combustion models are available. The energy and mass for burning solids or liquids must be input. It has no agglomeration model nor ability to represent log-normal particle-size distribution.

9.2.1.11 HGsystem 3.0 (Release and Dispersion) HGSystem is a general purpose PC-based, chemical source term and atmospheric dispersion model. It is comprised of individual modules used to simulate source-terms, near-field, and far-field dispersion. The chemical and thermodynamic models available in HGSystem include reactive hydrogen fluoride and nonreactive, two-phase, multicompound releases. It accounts for HF/H2O/air thermodynamics and cloud aerosol effects on cloud density, pressurized and non-pressurized releases, predicts concentrations over a wide range of surface roughness conditions and at specific locations for user-specified averaging periods, steady-state, time-varying, and finite duration releases, and crosswind and vertical concentration profiles. HGSystem offers the most rigorous treatments of HF source-term and dispersion analysis available for a public domain code. It provides modeling capabilities to other chemical species with complex thermodynamic behavior. It treats: aerosols and multi-component mixtures, spillage of a liquid non-reactive compound from a pressurized vessel, efficient simulations of time-dependent 354


dispersion by automating the selection of output times and output steps in the HEGADAS-T., improved dosage calculations and time averaging (HEGADAS-T/HTPOST), ability to model dispersion on terrain with varying surface roughness, effects of dike containments (EVAP), upgrade of evaporating pool model, user friendliness of HGSystem, upgrading of post-processors HSPOST and HTPOST, shared input parameter file. It is one of the few codes with a rigorous treatment of therrnodynamic effects and near field transport in vapor dispersion. The underlying computational models and the user input and processing instructions are well documented. It has been validated with large-scale field data. HGSystem cannot be used for analyzing releases where there is pipework present between the reservoir and the outlet orifice. There are a limited number of pool substrate materials which can be modeled by HGSystem, specifically sand, concrete, plastic, steel, and water. It is difficult to extend the physical/chemical database utility DATAPROP to include additional chemical species. Such modifications would require an extremely good knowledge of the HGSystem program structure and some consultation with the code developers. User expertise is needed for the range of computational options, extensive input data and large number of models. Source term improvement is needed for modeling highly stable meteorological conditions (e.g., pool evaporation for a i m/s, F stability wind field). Low momentum plumes, in general, are difficult to model. Releases from pipes cannot be calculated by HGSYSTEM. Liquid aerosol rainout is not modeled; aerosols are assumed to remain airborne until complete evaporation. The user's manual is Post (1994a); model references are: Clough (1987), Colenbrander (1980) DuPont (1988) Post (1994b), Schotte (1987) Schotte (1988) Vanderzee (1970), and Witlox (1993). Sponsor: Shell Component models Industry Cooperative HF Mitigation/Assessment Program, Ambient Impact Technical Subcommittee (HGSYSTEM Version 1.0), American Petroleum Institute (HGSYSTEM Version 3.0). Developer: Shell Research Limited Shell Research and Technology Centre Thornton, P.O. Box 1, Chester, CHI 3SH. Custodian: HGSYSTEM Custodian Shell Research and Technology Centre Thornton, P.O. Box 1, Chester, CHI 3SH, UK, Phone: 44 151 373 5851 Fax: 44 151 373 5845, E-mail: [email protected]. simis.com. The program and technical reference manuals are available through the American Petroleum Institute (API), National Technical Information Service (NTIS), and Shell Research Ltd. Computer: The code is intended for compilation under Microsoft FORTRAN Powerstation with PC execution, but may be adapted to any FORTRAN 77 compiler. It runs on a PC with a 386 CPU, 4 MB of RAM, 2 MB hard disk, math coprocessor recommended. Cost: None.

9.2.1,12 HOTMAC/RAPTAD (Dispersion) HOTM AC/RAPTAD contains individual codes: HOTMAC (Higher Order Turbulence Model for Atmospheric Circulation), RAPTAD (Random Particle Transport and Diffusion), and computer modules HOTPLT, RAPLOT, and CONPLT for displaying the results of the calculations. HOTMAC uses 3-dimensional, time-dependent conservation equations to describe wind, temperature, moisture, turbulence length, and turbulent kinetic energy. Its equations account for advection, Coriolis effects, turbulent heat, momentum, moisture transport, and viscosity. The system treats diurnally varying winds such as the land-sea breeze and 355


slope winds. The code models solar and terrestrial radiation, drag and radiation effects of a forest canopy, and solves thermal diffusion in soil. RAPTAD is a Monte Carlo random particle statistical diffusion code. Pseudoparticles are transported with the mean wind field and the turbulence velocities. HOTM AC/RAPT AD requires very extensive meteorological and terrain data input The program user's guide and diagnostics are inadequate. HOTMAC does not model multiple scale eddy turbulence and does not provide for dispersion of gases that are denser-than air. It must be tailored to reflect the climatic characteristics of specific sites. Sponsor: U.S. Army Nuclear and Chemical Agency. Developer: Los Alamos National Laboratory (LANL). Custodian: Michael D. Williams, Los Alamos National Laboratory Technology & Assessment Division TSA-4, Energy and Environmental Analysis, Los Alamos, New Mexico 87545, Phone: (505) 667-2112, Fax: (505) 665-5125, E-mail address: [email protected] 9.2.1.13 KBERT, Knowledge+Based System for Estimating Hazards of Radioactive Material Release Transients (Release) The current prototype code, is included because of being knowledge-based and its potential relevance for chemical releases. Presently, it calculates doses and consequences to facility workers from accidental releases of radioactive material. This calculation includes: specifying material at risk and worker evacuation schemes, and calculating airborne release, flows between rooms, filtration, deposition, concentrations of released materials at various locations and worker exposures. Facilities are modeled as a collection of rooms connected by flowpaths (including HVAC ducts). An accidental release inside the facility is simulated using the incorporated Mishima database as a relational database along with databases of material properties and dosimetry and mechanistic models of air transport inside the facility that use user input flow rates. Aerosol removal is currently gravitational settling. Filters may be modeled in any flowpath. Evacuation plans for individual workers or groups of workers can be specified. Radiological dose models include cloudshine, inhalation, groundshine, and skin contamination pathways with allowance for protective equipment. Output includes airborne and surface concentrations of released material throughout the facility, whole-body and organ-specific worker doses. A simulation begins by specifying the hazardous materials and scenario in an event dialogue. An intuitive dialogue box interfaces with the Mishima database to provide either a one time airborne release fraction or a continuous airborne release rate and respirable fractions for the materials involved in accidents such as fires, explosions, and spills. The code tests and limits input to "only realistic combinations" of release data, materials at risk, and accident stresses. This program is an integrating tool. Other than the dynamics of the air flow and settling of material, the program makes heavy use of databases for information concerning characteristics of releases, health effects and health models, therefore it could be adapted to chemical releases. The program is menu driven with easy change of input and default parameters. Modeling of a facility is relatively easy and the facility model can be stored. Once a facility has been modeled, part of it can be used for any particular accident scenario. As it stands, this program calculates the expected worker dose from an accidental release of radioactive material within the confines of a facility. The 356


code assumes that released material is mixed instantaneously in a room, so concentration gradients are not available. However a room can be broken into smaller volumes to get around this.- Aerosols settle only by gravitational settling without agglomeration. The manual indicates, that other deposition mechanisms can be "readily" implemented. The model is described in KBERT (1995) the release fraction reference is Mishima (1993). Sponsor: DOE/EM, Developer: Sandia National Laboratories, Custodians Dr. S.K. Sen, U.S. Department of Energy, Office of Environment, Safety, and Health, EH-34,19901 Germantown Road Germantown, MD 2087-1290 Phone: (301) 903-6571 Fax: (301) 903 4672, E-rnail: subir.sen® hq.doe.gov. Dr. K.E. Washington, Sandia National Laboratories, P.O. Box 5800, Albuquerque, NM 87185, Phone: (505) 844-0231, Fax: (505) 844-3296, E-mail: [email protected]. Computer: an IBM compatible PC with 386 CPU, 486 preferred, Windows 3.1, VGA graphics display (SVGA preferred) mouse and a hard disk with at least 10 MB free space. Tt is written in Microsoft Visual C++, Cost: unknown. 9,2.1,14 MISM, Modified IHe-Springer Model (Release) The MISM model is an evaporation and dispersion model specifically for hydrazine (N2H4), monomethylhydrazine (MMH), and unsymmetrical dimethyl hydrazine (UDMH) ground spills. However, it is useful for modeling the release of other toxic, flammable, or explosive materials. It predicts the rate of evaporation from a pool of spilled liquid by estimating a mass transfer rate which is determined from the vapor pressure of the pure liquid, the diffusive properties of the vapor at the air-liquid interface, and the wind generated turbulence over the pool. The model assumes: the spill occurs without atomization; the spill is adiabatic and the liquid is chemically stable; the spill occurs onto a flat non-porous surface; evaporation occurs at a steady state pool temperature; the spill is a pure liquid; and ideal gas behavior of the vapor film. The steady-state pool temperature is determined by iterating energy balance that equates heat inputs (convective heating from the ground and atmosphere, solar insolation and radiative heat transfer from the atmosphere) with heat losses (radiative emission from the pool and evaporative cooling) to establish the equilibrium vapor pressure of the liquid. The separation of this equilibrium vapor pressure from the steady-state vapor concentration that develops at the pool interface establishes the concentration driving force for evaporation. A mass transfer coefficient equates the driving force to the mass transfer rate. The mass transfer coefficient is a complex function of the wind speed, the degree of atmospheric turbulence, and the pool diameter. The properties of the evaporating vapor enter through a Schmidt number. A derivation of the model and examples of input development are given in Appendix A to the user manual. A simple, point source Gaussian model without any buoyancy or plume rise effects is used to calculate dispersion and downwind concentration of the releases. The dispersion coefficients, oy and oz, are based on Turner, 1970. The user's manual is Ille (1978). Other references are Mackay (1973), Kunkel (1983), Schmidt (1959), and Bird, (1966).

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Sponsor/Developing Organization: Department of Defense, Civil and Environmental Engineering Development Office, Tyndall Air Force Base, Panama City, Florida, 32403. Computer: The code is 200 lines of FORTRAN, hence, it should compile and run on most PC. Cost: Unknown, 9.2.1.15 Army ORG40/TP10 (Part EVAP4.FOR of D2PC) This is a subroutine that calculates an evaporation rate from a pool of spilled liquid in presence of wind (ORG-40), or in still air (TP-10). It was developed by the U.S. Army for downwind hazard prediction following release from smoke munitions and chemical agents. The code calculates the evaporation rate of a liquid pool, given the physical state variables, wind speed, and diameter of pool. ORG-40 and TP-10 models are coded as a Fortran 77 subroutine, EVAP4.FOR, in D2PC. The user's manual is Whitacre (1987). Sponsor/Developing Organization: U.S. Army Chemical Research and Development Engineering Center, Aberdeen, MD Custodian: Commander, U.S. Army CRDEC, Aberdeen Proving Ground, MD 21010-5423. 9.2.1*16 PHASTProfessional (Commercial - Release and Dispersion)

Fig. 9.2-1 Case Study Refinery and Town

Fig. 9.2-2 Input to Phast

PHASTProfessional uses a user-friendly Windows interface to link source-term, dispersion, fire, and explosion models. The output is text and color contour. It models pool boiling evaporation, two-phase releases (flashing, aerosol formation, and rainout), free jet plumes and fires, BLEVEs, and vapor cloud explosions. It facilitates data entry with complete model references and user guide documentation. Some model validation has been conducted against large-scale field and wind tunnel data. Graphical results (e.g., cloud footprints) can overlay on a map background, for assessing affected zones in a consequence assessment. 358


Case Study: A refinery is five kilometers from a small town on a flat plain at 10 meters elevation surrounded by arable farmland (Figure 9.2-1). Summer temperatures are about 20° C with 70% relative humidity. The refinery contains a large alkylation unit with hydrogen fluoride, LPG and alkylates in large quantities. The concern is the control room and safety in the town. Previous studies of the hydrogen fluoride risk have not accounted for its oligorneric behavior. The LPG consists of 40% butane and 60% propane. The HF is stored in a 150 tonne tank with an alkylation reactor over the tank. Both the LPG and the HF are stored at ambient temperature without dikes or building enclosure. While all possible scenarios, identified by HAZOP, must be considered, a leak of HF from a thermowell in the acid circulation leg of the reactor (3 cm) and a cold release of LPG from a feed pipe to the reactor (6 cm) are of particular interest. The LPG is maintained at atmospheric pressure and the thermowell is situated toward the bottom of the reactor at a liquid head pressure of about 4 meters. Various measures can be used to gauge the threat posed by toxic (HF) and flammable (LPG) consequences of these releases. Emergency Response Planning Guideline (ERPG) concentrations levels are designed to assist the preparation of off-site emergency plans. A number of toxic correlations can be used to determine the incidence of fatality resulting from exposure to the cloud. Heat radiation effect levels can be set to different levels to model different levels of damage. It contains these toxic and flammable data in its database. Figure 9.2-2 shows a data input screen in which general characteristics are input by radio buttons and numerical data is typed. The program calculates distances to specified toxic concentrations and other requested consequence levels automatically. Results are available in a variety of formats including cloud footprints, sideview, cross section, pool evaporation rate, concentration vs distance and heat flux contours. Figure 9.2-3 shows the calculated results as a toxic plume superimposed on the map with and without oligomerization. Although the code is based on well-recognized models referenced in the literature, some of the underlying models are based on "older" theory which has since been improved. The code does not treat complex terrain or chemical reactivity other than ammonia and water. The chemical database in the code is a subset of the AIChE's DIPPR database. The user may not modify or supplement the database and a fee is charged for each chemical added to the standard database distributed with the code. The code costs - $20,000 and requires a vendor supplied security key in the parallel port before use. Sponsor/Developer: Det Norsk Veritas, http://www.dnv.com/technica. Custodian: DNV Technica, Palace House, 3 Cathedral St., London SEl 9DE, UK, Phone +44(0)171 716 6545, or DNV Technica Inc., 40925 Country Center Dr. Suite 200, Temecula, CA 92591, (909) 694-5790., Computer: Windows 3.x, '95, or NT, 40 MB hard drive, 16 MB RAM. Cost: Depends on type perpetual license, fixed period license, non-commercial academic are available. For example, one-year lease including upgrades, training, and technical support is $11,500. 9.2.1.1? Pspiil (Release) PSpill determines the mass airborne from a spill of solid powder. It models the shearing effect of the air on the powder as it falls. The shearing effect is enhanced by the lengthening of the 359


graph

PHAST Graphing Edit

Options

Window

Graph - Model: HF {No oiigomerisation] - Weathj»

Graph - Model: HF (With oligomerisation) - We a]

Fig. 9.2-3 Calculated Toxic Plumes on Map

spill column caused by the acceleration of gravity. The mass of material that becomes airborne from a spill of powder is assumed proportional to the drag force on the powder as it falls. The growth rate of the powder front is constant and can be characterized by an angle of dispersion. The diameter of the powder front at the start of the spill is equal to the diameter of the container from which it was spilled. The model assumes that any airborne material created as a result of impact with a surface is negligible, and ignores airborne particulate generated as a result of impact. Its model applies only to powders for bulk spills, not continuous pours using experimental data from NUREG/CR-2139 NUREG /CR-4658. The model is described in its users manual: NUREG/CR-4997. Sponsor /Developing Organization: Pacific Northwest Laboratory, P.O. Box 999, Richland, WA 99352, Custodian: Marcel Ballinger, Pacific Northwest Laboratory, P.O. Box 999, Richland, WA 99352. Phone: (509) 373-6715 Computer: The original code was written in FORTRAN, to run on a VAX minicomputer, but can be rewritten to run on most any platform. Cost: None. 9.2.1.18 SLAB (Dispersion) SLAB is one of the most widely-used dense gas models in the public domain. The model accepts evaporating pool sources, jet releases at any elevation, and instantaneous volume sources.

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SLAB calculates chemical concentrations at positions downwind and heights above the ground. The plume may be denser-than-air, neutrally-buoyant, or less dense than air. Thermodynamics effects are accounted for, including latent heat exchanges due to the condensation or evaporation of liquids, Time averaged results may be calculated. SLAB is the easiest of the publicly-available dense gas models to set up and run. It has been extensively validated against large-scale field data, It does not calculate source emission rates. While it handles jets, it does so simply and does not calculate the details of the jet motions and thermodynamics. It should not be used for strongly buoyant plumes. The error diagnostics are limited to checking the consistency of input parameters. Run time error diagnostics are missing but are rarely needed due to its robustness. Sponsor/Developing Organization: Department of Energy (DOE)TLawrence Livermore National Laboratory (LLNL). It is distributed and supported by the EPA and by Bowman Environmental Engineering. Custodians: EPA UN Bulletin Board, Phone (919) 541-5742. An enhanced and user supported commercial version of SLAB is available from Bowman Environmental Engineering, P.O. Box 29072, Dallas, TX 75229, (214)233-5463. Cost: None. May be downloaded from EPA's web site: http://www.epa.gov/scramOQ 17t22.htm. Look under "non-EPA files.for SCREEN2C - SCREEN2C - contains Schulman-Scire cavity algorithm (150kB ZIP) 9.2.1.19 TSCREEN (Release and Dispersion) TSCREEN (A Model of Screening Toxic Air Pollutant Concentrations) analyzes toxic emissions and subsequent dispersion from many different types of releases. It is a simple, conservative screening tool for obtaining maximum downwind vapor concentrations at select receptor locations for releases resulting from a) particulate releases, b) gaseous releases, c) liquid releases, and d) superfund releases. A particular release scenario is selected via input parameters, and TScreen automatically selects and executes the appropriate dispersion model to simulate that scenario. The model to be used and the worst case meteorological conditions are automatically selected. It has four imbedded air toxin dispersion screening models, SCREEN2, RVD, PUFF, and the Britter McQuaid model. The release scenario is defined by the input parameters; it automatically selects and executes the dispersion model for the scenario. SCREEN2 is a Gaussian dispersion model applicable to continuous releases of particulate matter and nonreactive, nondense gases that are emitted from a point, area, volume, and flared sources. The RVD model provides short-term ambient concentration estimates for screening pollutant sources that release vertically-directed, denser-than-air gases and aerosols. The PUFF model is used where the release duration is smaller than the travel time. The Britter-McQuaid model is used for continuous and instantaneous denser-than-air scenarios. The program is a screening tool, some of the models are overly conservative in .*he source-term and downwind dispersion. The most conservative models are superheated flashing releases and unconfined liquid pool evaporation. Furthermore, it only computes steady-state release rates, assuming ideal state conditions. Releases must fit into one of several scenarios that are defined in the workbook. If input parameters are not consistent with the selected category, a new category may be suggested and the model starts over with the input requests. The user cannot define meteorological conditions and cannot select which of the models to use. The

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Sponsor/Developing Organization: EPA, Research Triangle Park, NC Custodian; Lawson, Jr., U.S. Environmental Protection Agency, Research Triangle Park, NC 27711, Phone: (919) 541-1199, or Jawad Touma, Project Officer US EPA, (3AQPS, TSD (MD-14) Source Receptor Analysis Branch, Research Triangle Park, NC 27711, Phone: (919) 541-5381, Computer: PC with 286 or higher CPU, 570 kB RAM and 2 MB on the hard drive. Cost: None. May be downloaded from EPA's website: http://www.epa.gov/scram001/t22.htm. Look under "non-EPA files" for SCREEN2C-SCREEN2C, contains Schulman-Scire cavity alg.(150kB ZIP)

9.2.1.20 VDI 3783 Parts 1 & 2 (Dispersion) VDI Part 1 models the dispersion of vapor plumes with output consisting of vapor concentration as a function of time and downwind distance and denser-than-air vapor releases. VDI Part 2 determines the downwind distance to the lower flammable limit of a combustible vapor. Part 2 may also be used in conjunction with Part 1 to model a toxic gas emission. Part I is a computerized implementation of the Gaussian plume equations for continuous ground-level or elevated release. The release rate may be time varying within specific prescribed constraints on variability. Reflection of the plume off the mixing layer lower boundary is also modeled. Point, line, area, and volume source geometries may be modeled using the code. Part 2 predicts the dispersion of denser-than-air gases based on empirical data obtained from wind-tunnel studies for puff and continuous releases into boundary layer shear flow. The model is applicable for level, unobstructed dispersion as well as more complex flow and turbulence structure due to the presence of downwind obstacles. Part 1 assumes complete reflection of the plume at ground level and in the mixing layer. Volume sources are initially approximated as right parallelpipeds. The modeling of line, area, and volumetric vapor sources is not an accurate solution of the diffusion equation and may give inaccurate results in downwind concentration estimates when the dimensions of the source are not much less than the downwind distance of interest. Part 2 assumes dense gas releases are ground-level point sources released into an ambient temperature of 20 ° C. Heat transfer effects typically present in dense gas dispersion are not modeled in the code. Sponsor/Developing Organization: Verein Deutscher Ingenieure (VDI) Komrnission Reinhaltung der Luft, D-4000 Dusseldorf, Deutschland. Custodian: Dr. Michael Schatzmann Meteorologisches Institut Universitat Hamburg, Bundesstrase 55 D-20146 Hamburg, Germany, Telephone: 49-40-41235040, Telefax: 49-40-41173350.

9.2.2 Explosions and Energetic Events 9.2.2.1 EXPAC EXPAC analyzes an interconnected network of building rooms and ventilation systems. A lumped-parameter formulation is used that includes the effects of inertial and choking flow in rapid gas transients. The latest version is specifically suited to calculation of the detailed effects of explosions in the far field using a parametric representation of the explosive event. A material transport capability models the effects of convection, depletion, entrainment, and filtration of 362


explosions in the far field using a parametric representation of the explosive event. A material transport capability models the effects of convection, depletion, entrainment, and filtration of material. The effect of clogged filter systems on the gas dynamics is accounted for in the model. The air-transported contaminant material is restricted to a single phase for a single species. No phase transitions or chemical reactions are modeled in the code. If the contaminant is an aerosol (solid or liquid), then it is treated as a monodisperse and homogenous spherical particle. Material transport initiation may be user-specified or calculated via aerodynamic entrainment. Setting up the problem is tedious. Flow resistance coefficients must be estimated for the ventilation components. The user's manual and model reference is Gregory and Nichols (1991). Sponsor/Developing Organization: LANL. Developer: W.S. Gregory and B.D. Nichols, Custodian: LANL/W.S. Gregory Telephone (505) 667-1120. Hardware: CRAY mainframe computer, 32K. words of storage for the executable module, run time: several minutes (real time). Language: FORTRAN. Portability: Designed for portability to other computer platforms if the word length is less than 64 bits, double precision in the solution modules of the code may be needed to retain comparable accuracy. Comment statements regarding the input and output formats and a complete glossary of variables are included in the source code to facilitate later modifications. Cost: None, 9.2.2.2 GASFLOW GASFLOW models in-facility transport and vapor space combustion by solving the 3-D compressible Navier Stokes equations and the transport equations for internal energy and chemical species. The geometry is made discrete by a mesh in Cartesian or cylindrical geometry. The primary hydrodynamic variables in the final analysis are the cell-face-centered nominal velocity and cellvolume-centered density, internal energy, and pressure. Three different turbulence models are available for modeling turbulent diffusivity: algebraic, subgrid-scale, and k-e. The model that accounts for heat transfer between the convective flow streams and the facility walls or structures can treat enhanced transfer rates associated with high mass fluxes toward the walls. No solid or liquid combustion model is available. The energy and mass source for burning solids and liquids must be input. Assumptions are: each cell is well mixed, all gases are assumed to be ideal, and choke flow in the ventilation system components is not considered. It treats multidimensional flow multispecies diffusion, including chemistry models with capability for modeling diffusion flame and flame propagation through vapor spaces having complex geometry. The user's manual is: Travis et. al. (1994, Volume 2), the model description is in Volume 1 and comparisons with field experiments is in Volume 3. Sponsor/Developing Organization: DOE-DP, DOE-EM, and NRC. Custodian: Kin Lam M/S K575 LANL, Fax: (505) 665-0879, E-mail: [email protected]. Hardware: CRAY (UNICOS) mainframe computer, SGI (UNIX) workstations, and SUN (UN) workstations. Computer memory requirements depend on the problem size and can be large for complex problems. Runtimes on the CRAY vary from a few seconds to several hours. Typical runtimes for Hanford waste tank burp and burn problems. Software: FORTRAN NAMELIST feature specifies all model option selections and numerical data. Input is tested for valid range and self-consistent user options. The post-processor

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graphics library assessed by GASFLOW is only available at LANL. Therefore, porting the code to other platforms would require, in part, disabling any program calls to the graphics routines and providing alternate graphics capabilities. Cost: Not presently available. 9.2.2.3 HOTSPOT/Version 8.0 HOTSPOT provides a fast, field tool for evaluating accidents involving radioactive materials. It consists of 4 main computational modules: radioactive source-terms generated by explosions, radioactive source-terms generated by fires, resuspension of radioactive material, and a Gaussian dispersion model to estimate the transport of radioactive material in a continuous plume (puff) release. The blast overpressure models are based on TNT-equivalency methods or empirical correlations derived from experimental tests involving the detonation of nuclear materials. Blast overpressure calculations are performed for conventional and nuclear weapons. Radiation exposure due to an energetic release of plutonium, uranium, and tritium is also calculated. The later is based on a user-supplied release fraction where the energy of the blast is used to determine the loft height of the material and the Gaussian dispersion equations are used to determine the airborne exposure, It is easy to use for estimating radiation, thermal, and blast overpressure exposure as a function of distance from the source event, but simplicity does not handle energetic events in complicated scenarios, e.g., partial containment by a structure, blast wave enhancement or damping due to the presence of nearby structures. The user's manual and reference is Homann (1994). Other documentation is Nadeau (1995a-c). Sponsor/Developing Organization: LLNL. Developer: Steven G. Homann, LLNL L-380, P.O. Box 808, Livermore, CA 94551 Phone (501) 423-4962, Fax: (501) 423-3090, E-mail: [email protected]. Custodian: Same. Hardware; IBM PC compatible with a 80286 processor or greater, 512 kB of RAM, Microsoft DOS version 3.0 or later, Math coprocessor chip is desirable optional, but highly recommended, 0.5 MB hard disk space. Software: Pascal, typical run time several seconds. Cost; No charge from LLNL. 9.2.2.4 CHEETAH 1.40 CHEETAH is a thermo-chemical code that implements the Chapman/Jouget (C-J) detonation theory in a PC based calculational model. It consists of a standard model for evaluating explosives and propellants. In C-J theory the detonation point is in thermodynamic and chemical equilibrium; Cheetah solves thermodynamic equations between product species to find chemical equilibrium. It can calculate thermodynamic states where the pressure and temperature are not explicitly indicated. From these properties and elementary detonation theory, detonation velocity and detonation energy are predicted. It includes a gun and a rocket model for evaluation of propellant formulations, and predicts concentrations and properties of reaction products. It is recommended for evaluating simple fuels to high explosives for predicting energy release and reaction by-products concentrations. CHEETAH does not consider finite size effects in explosives predictions; condensed products are poorly parameterized for far from ambient conditions which may overestimate the detonation

364


velocity for materials producing large concentrations of condensed products. References are Fried a and b. Sponsor/Developing Organization: LLNL. Developer: Laurence E. Fried LLNL, P.O. Box 808 Livermore, CA 94551, E-mail: [email protected]. Hardware; IBM-PC or clone, Windows 3.1, Windows 95, Mac OS 7.x or later, SUN and SGI workstations, 4.3 MB of hard disk. Software: ANSI C. Run execution time for typical problem (CPU or real time). Standard run: About 30 seconds on a Power Macintosh 6100/80. Cost: None from LLNL. Source code is available, with the stipulations that all modifications be preapproved and forwarded to the sponsor for tracking

9.2.3 Fire Codes 9.2.3,1 FIRAC/FIRIN FIRAC/FIRIN predicts the distribution of temperatures, pressures, flows, and toxic materials within a facility. It models the movement of hazardous materials between gloveboxes, rooms, and cells connected by ventilation systems to assess the release within such compartments. It uses a source submodule called FIRIN for modeling of user specified parameters such as energy, temperature, pressure, or mass addition. As such, it can be used to model the release concentration of hazardous material within a burning room and in connecting compartments to determine the building source term. The FIRIN submodule calculates the mass generation rate and the size distribution of airborne material released by fire accident scenarios. FIRIN calculates the mass and energy input to FIRAC. The FIRAC/FIRIN combination evaluates the source terms within and from a facility. It has a graphical user interface for drawing a representation of a particular fire scenario and the ventilation system involved. As picture elements are added, input windows open automatically to allow the input of information. When the graphical model is complete, including the required data, the preprocessor automatically generates the required input file. FIRAC/FIRIN capabilities and models are divided into the following major categories: Gas dynamic models, material transport models, heat transfer models, fire models, and source term models. The user's manuals are: Nichols and Gregory (1986) Chan et al. (1989). Benchmarking references are: Allison (1992), Gregory (1989), Alvares, (1984), Nichols (1986), and Gregory (1991). Validation against experiment: Claybrook(1992) Sponsor: U.S. Nuclear Regulatory Commission (NRC). Developing Organizations: the NRC with Los Alamos National Laboratory, Westinghouse-Hanford Company, and New Mexico State University. The fire compartment model within FIRAC/FIRIN (called FIRIN) was originally developed by Battelle Pacific Northwest Laboratories and extensively modified before incorporation. Original Developer: B. D. Nichols and W.S. Gregory, LANL. Current Custodian: W.S. Gregory, LANL, phone (505) 667-1120. Hardware Requirements: IBM-PC or comparable VGA graphics, math coprocessor with an 80386 or better CPU, 5.25 or 3.5 inch high density disk drive to install the distribution disk, a mouse recommended. Software DOS 3.X or higher, SVS FORTRAN to change the source code. Cost: None through LANL.

365


9.2.3.2 CFAST CFAST, within zonal model limitations, solves the mass and energy conservation equations to estimate compartment temperatures and species concentrations in a burning facility. The front-end module, Cedit, allows the user to develop the input deck via as series of menus. CPlot, a post-processing module, generates on-screen and hard copy plots of the data. It lacks a fire growth model, however, specific fire-related physics dealing with hot gas layers, fire plumes, door jets, radiative heat transfer, and ignition of secondary fires are modeled. In addition, a building ventilation system (ducts, vents, and fans) can be included in a facility model. CFAST can generate tabular (ASCH) and HPGL graphics output. The variables that are output are: layer interface height, upper and lower layer temperature, surface (walls, floors, ceilings) temperatures; pressure; fire locations; optical density; some flow rates, and species concentrations. Limitations are: it requires a priori specification of the temporal behavior of the fire; does not calculate radiological source terms; assumptions in the zone model formulation of the conservation equations; does not output all important variables; does not model mitigative systems, and deficient documentation. The user's manual and methodology is Portier (1992); the methodology, source code verification and benchmarking reference is Peacock (1993a). Validation against experimental data is reported in: Peacock (1993), Jones and Peacock (1994) and Jones (1994). Sponsor: NIST Building and Fire Research Laboratory. Developing Organization: Same. Original Developer: Same. Current Developer and Custodian: Walter W. Jones ,NIST Building and Fire Research Laboratory, Gaithersburg, MD 20899. Hardware: IBM-PC compatible 386 or better, with at least 2.5 MB of free extended memory, VGA graphics; or Silicon Graphics machine. Software: MS-DOS 5.0, or higher, or Windows 3.xx or Silcon Graphics IRIX 4.0.5 or 5,xx. Cost: None, it is supplied on two 3.5 inch disks. 9.2.3.3 FPEtooJ FPEtool consists of the modules: SYSTEM SETUP is a utility for changing file destination, source directories, operating units, and screen colors. FIREFORM is a collection of quick procedures that solve single-parameter questions, e.g. ceiling jet temperature, mass flow through a vent, upper layer temperature, etc. It treats temperature variation and smoke layer descent, atrium smoke temperature, buoyant gas head, ceiling jet temperature, ceiling plume temperature, egress time, fire/wind/stack forces on a door, lateral flame speed, effective time of thermal resistance, mass flow through a vent, plume filling rate, radiation ignition of a near fuel, smoke flow through an opening, sprinkler/detector response, energy requirements for flashover, upper layer temperature, and ventilation limits. MAKEFTJRE models the growth, steady state, and decay phases of the each fuel element in the compartment. It consists of routines that create and edit fire files that specify the fire heat release rate and fuel pyrolysis rate as a function of time.

366


FIRE SIMULATOR predicts the effects of fire growth in a 1-room, 2-vent compartment with sprinkler and detector. It predicts: temperature and smoke properties (O2/CO/CO2 concentrations and optical densities), heat transfer through room walls and ceilings, sprinkler/heat and smoke detector activation time, heating history of sprinkler/heat detector links, smoke detector response, sprinkler activation, ceiling jet temperature and velocity history (at specified radius from the fire), sprinkler suppression rate of fire, time to flashover, post-flashover burning rates and duration, doors and windows which open and close, forced ventilation, post-flashover ventilation-limited combustion, lower flammability limit, smoke emissivity, and generation rates of CO/CO, pre- and post-flashover. CORRIDOR calculates the characteristics of a moving smoke wave. 3rd ROOM predicts smoke conditions developing in a room and the time to human untenability from heat and inhalation exposure. FPEtool is described in Deal (1995). No formal benchmarking has been performed, nor has any source code validation or validation against experimental data but the code is based on a number of experiments: Notarianni (1993), Walton (1993), Nelson (1992), Peacock (1993b), Heskestad (1986) and Hinkley( 1975). Sponsor: GSA, Public Building Service, Office of Real Property Management. Developing Organization: NIST Building and Fire Research Laboratory, Gaithersburg, MD 20899. Original Developer: Same. Current Custodian for Development: Walter W. Jones, Group Leader Fire Modeling and Applications Group, Building and Fire Research Laboratory, NIST, Gaithersburg, MD 20899, Phone: (301) 975-6887. Distribution: Richard Bukowski, Fire Research Information Services, Building and Fire Research Laboratory, NIST Gaithersburg, MD 20899-001 Phone: (301) 975-6853. Hardware: IBM PC compatible computer with an 8086 or higher CPU, a minimum of 640 kB RAM, and 3 MB of hard-disk space. CGA graphics or better. A math coprocessor is recommended. Software TSCREEN needs DOS version 3.1 or higher. It runs under Windows. To modify and compile FPEtool, Microsoft QuickBasic v7.0, or equivalent is needed as well as the BASIC source code. 9.2.3.4 COMPBRN III COMPBRN ffl is a single-room zone fire model for probabilities risk assessment calculations. It models fires in an open or closed compartment using a 2-layer zone model approach. Thermal radiation and flame propagation are included. It requires a large amount of input: room geometry ventilation, doorway information, fuel bed geometry, orientation, thermal and combustion properties, ignition fuel location and properties, ignition temperatures of fuel, burning rate as a function of incident heat flux (surface-controlled burning) or ventilation (ventilation-controlled burning), and a definition of which fuel elements exchange thermal radiation with each other and with ceiling and walls. It outputs: total mass burning rate, total heat release rate, hot gas layer temperature and depth, indication of fuel cell damage and burning, radiative and total heat fluxes to targets, fuel cellmass, flame height over each fuel cell, flame temperature over each fuel cell, fuel cell temperature, and heat transfer coefficient (convective) for each cell. It only is applicable to single-room, pre-flashover fire compartments. Quasi-steady state assumptions are made; it is highly 367


dependent on experimentally determined parameters. It has no spatial resolution of temperature gradients nor fire suppression models. Flame spread occurs along discrete elements, and requires user input of burning rate parameters. It has a flame spread model, runs quickly, and calculates thermal radiation to targets. It applies to small fires for which correlations are generally applicable, simple compartment geometries, and not to fast-transient fires. The user's manual is fto (1985). Related references are: Chung (1985), Siu (1980), Siu (1982), Sui and Apostolakis (1982), Siu (1983), Lambright (1989), and Nicolette (1989). Sponsor: USNRC. Developing Organization: Mechanical Engineering Department, University of California at Los Angeles. Original Developer: G. Apostolakis, N. Siu, V. ho, G. Chung Current Custodians: EPRI has latest utility version, COMPBRN 3-e; Prof G. Apostolakis, MIT, has COMPBRN III (presumably public domain). Hardware: IBM PC or clone with 386 CPU or better or a Workstation. Software: FORTRAN Compiler, Text Editor if code modifications are needed. Cost: Nominal for disks and manuals, may be more restricted from EPRI. 9.2.3.5 VULCAN VULCAN is applicable to internal compartment fires, external pool and jet fires. It uses finite difference methods to solve governing equations. Included are combustion, soot, turbulence, and thermal radiation models. Its "first-principles" approach solves the basic conservation equations. The model reference is: Holen (1990); user's manual reference is: Karneleon and Kameleon. The source code verification is available for review from V. Nicolette at SNL. References for validation against experimental data: Holen (1990); Gritzo (1995a); Gritzo (1995b). Current plans are to extend the model to multiple fuels, including solid material, and to include suppression models (both gaseous inerting and water sprays). The model has been applied extensively to fires in compartments, on offshore oil platforms, and pool fires. This model is at the forefront of the science of fire modeling. Sponsor: Norwegian Oil and Gas Industries and U.S. Defense Nuclear Agency. Developing Organization: SINTEF (Norway) and SNL. Original Developer: SINTEF (Norway) arid Norwegian Institute of Technology (NTH). Current Custodian: SINTEF and SNL. Hardware: Workstation preferably silicon graphics to take advantage of integrated graphics and calculations. The larger (i.e., faster) the computer the better. Software: FORTRAN Compiler, C Compiler, Text Editor. See Holen, et al, previous reference. Cost: Not for sale, commercially, arrangements must be made with SNL and SINTEF.

9.3 EPA's Exposure Model Library and Integrated Model Evaluation System 9.3.1 IMES The U.S. Environmental Protection Agency concentrates on modeling the dispersion of toxic material in the environment and the health effects thereof rather than accident prevention. The

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EPA's Exposure Model Library and Integrated Model Evaluation System

reason for this is that most of the environmental problems are not due to accidents but to intentional or careless releases in a time when there was less concern for the environment. However in EPA's area of emphasis they are very comprehensive and most if not all of their models are in the public domain although contractor variations may not be. EPA, 1996,1 is the third edition of EML/MES on CD-ROM for distributing exposure models, documentation, and the IMES about many computer models used for exposure assessment and other fate and transport studies as developed by the EPA's Office of Research and Development (ORD). The disk contains over 120 models in files that may contain source and executable code, sample input files, other data flies, sample output files, and in many cases, model documentation in WordPerfect, ASCII text or other formats. The disk contains IMES with information on selecting an appropriate model, literature citations on validation of models in actual applications, and a demonstration of a model uncertainty protocol. The IMES software is an MS-DOS application capable of running on a network. Model codes and documentation can be downloaded from the CD-ROM to a hard drive. An MS-DOS interface is included to provide easy access to IMES and to the model directories, although such is not required to access the files. This third edition provides an HTML Interface for viewing the model directories and Internet sources of some the models. Note: The CD-ROM is provided as a means of model distribution. With a few exceptions, the models are not designed to run on the CD-ROM (although the IMES is). Many of the model files were originally designed for distribution from floppy diskettes or bulletin board systems; keep this in mind as you read the installation instructions which are provided in the model directories. These instructions have not been rewritten for installation from CD-ROM. In most cases, you can simply copy the files directly to a hard drive for execution of the model. Many files have been stored in a compressed format using PKZIP® from PKWARE, Inc. The directory PKZIP contains the pkunzip utility for extracting these files. For models distributed and maintained by the EPA Center for Exposure Assessment Modeling (CEAM), an installation directory may be provided; use the supplied installation program to install these models, because these programs check your hardware and software for possible conflicts. Getting Started The Exposure Models Library may be accessed either with the DOS EML interface program or with an HTML browser program such as Netscape or Microsoft Internet Explorer. To use the DOS EML interface and to access the IMES, enter the drive letter of your CD ROM drive, set the default directory to EML and then enter EML (e.g., D: CD\EML EML). From the menu, run or download the available models of IMES to your hard disk. Also you may access EML directories with your HTML browser by opening the EMLINTRO.HTM file in the root directory. The HTML

1

For copies of the CD or for technical assistance, call Richard Walentowicz at the EPA Office of Research and Development at 202-260-8922 [[email protected]). Information on individual models should be obtained from the model developers.

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files contain links to sites for many of the models that were on the Internet when the CD was produced. With Internet access, these links may be checked for model updates.

Table 9.3-1 Computer Models on the EPA Disk Air models

Groundwater models

Surface Water Models

Multimedia models

PHREEQE

CEQUALICM

PLUMES

MULTIMED

PHREEQER

CEQUALR1

QUAL2E

PATRIOT

BIOPLUMII

PRZM

CEQUALRIV1 RECOVERY

PTPLU

BTEX

RANDWALK CEQUALW2

BLP

MPTER

AT123D

CAL3HQC

OCD

BALANCE

CALINE3

PLUVUE2

CALPUFF

RESTMF

PCGEMS Other models

COM2

RAM

CHEMFLO

RETC

CORMIX

RIVMOD

FGETS,

CMB7

RPM

DBAPE

RITZ

EXAMS

SEDDEP

NRDAM

COMPLEX 1

RTDM

EPA-WHPA

RUSTIC

FATE

SMPTOX

PIRANHA THERdbASE

CRSTER

RVD2

FEMWATER STF

HEC5Q

THERMS

CTDMPLUS

SCREENS

OEOPACK

STFBASE

HEC6

WASPS

CTSCREEN

SDM

GLEAMS

SUTRA

MICHRIV

WQAM

DEGADIS

SHORTZ

HSSM

SWANFLOW MINTEQA2

WQRRS

EKMA

TOXLT

HST3D

SWIFT 1 1

WQSTAT

FDM

TOXST

MOC

TETRANS

ISC3

TSCREEN

MOCDENSE TRIPLOT

AGNPS

GWLF

LONGZ

UAM

MODFLOW

TWQM

ANSWERS

HELP

SWRRBWQ

MESOPUFF

VALLEY

MOFAT

VLEACH

CREAMS

HSPF

USGSREG

MPRM

VISCREEN MT3D

WATEQF

EPIC

P8-UCM

WEPP

WHEAM

EXPRES

PREWET

WMM

FHWA

SWAT

OASIS PESTAN

PCPROUTE

Non-point source models SWMM

System Requirements Needed are an Intel, or equivalent, personal computer with an ISO 9660 compliant CD ROM, hard disk with 8 MB available (to ran IMES on the hard disk), at least 540 kB of free RAM; VGA monitor or better. Operating System: MS DOS 3.1 or higher (for DOS EML). Windows 3.x or higher for Windows-based nonpoint source model selection module. The Exposure Models Library/IMES consists of a selection of fate transport and ecological models which can be used for exposure assessments in various environmental media. The models were developed primarily by various EPA offices and other federal agencies and are in the public domain. Models included are listed in Table 9.3-1. Model codes and documentation are contained within subdirectories for each category.

370


IMES was developed to assist in the selection and evaluation of exposure assessment models and to provide model validation and uncertainty information on various models and their applications. MES is composed of 3 elements: 1) Selection - a query system for selecting models in various environmental media, 2) Validation - a database containing validation and other information on applications of models, and 3) Uncertainty - a database demonstrating application of a model uncertainty protocol.

9.3.2 PIRANHA This directory contains the USEPA Pesticide and Industrial Chemical Risk Analysis and Hazard Assessment system. Documentation for PIRANHA is contained in a MANUALS subdirectory; enter PIRANHA C: where C: is a hard disk to receive the output files to run the system. For efficient operation of PIRANHA, transfer the files from the CD-ROM to your hard disk (it requires 28 MB). Data files are accessed from the CD-ROM when running PIRANHA.

9.3.3 REACHSCN ReachScan is a PC program package that aids an exposure assessor by bringing to PC's the Hydrologically Linked Data Files (HLDF) maintained by the Assessment and Watershed Protection Division (AWPD) of the Office of Wetlands, Oceans, and Watersheds (OWOW) of USEPA. HLDF in addition to others contains the files: REACH, GAGE, the Industrial Facility Discharge File (IFD), and the Water Supply Database (WSDB). These files contain information on rivers in the United States (their names, lengths, and flows), industrial dischargers, and drinking water supplies. Although capable of several functions, ReachScan's primary purpose is to: * • » «

Report public drinking water utility intakes located down river from a discharge point (an industrial facility). Report the distance between a discharge point and intake. Estimate the concentration of a discharged chemical at the intake point by: 1) simple dilution, or by a simplified degradation equation with dilution. Report the name of the down river water utility and the number of people served by it.

The program can also search upriver and downriver for industrial facilities starting from an industrial facility, water utility, or river segment. This directory also contains PDM3, a PC-based program to perform screening level exposure assessments. PDM3 predicts how many days per year a chemical at a concern level in an ambient water body will be exceeded after being discharged from an industrial facility,

9.3.4 S1DS The Select Industrial Discharge System (SIDS) assists exposure assessors and other analysts by consolidating current data contained in various EPA water-related environmental information 371


systems in one electronic database, SIDS contains data that have been selectively downloaded from nine existing information systems and is designed to provide a comprehensive database of facility, discharge, and receiving stream information for select industrial dischargers to surface waters in the United States,

9.3,5 THERDCD THERdbASE (Total Human Exposure Risk database and Advanced Simulation Environment) is a PC-based computer software that manages data and models. It has exposure, dose, and risk related data files organized in a Database Engine. Exposure, dose, and risk related models, that draw information from the Database Engine, are organized in a Modeling Engine. THERdbASE comes from an ongoing project with EPA's Office of Research and Development (National Exposure Research Laboratory, Las Vegas, NV) to develop a tool for making exposure, dose, and risk assessments. The Database Engine in THERdbASE has the following data groups: i) Population Distributions, 2) Location/Activity Patterns, 3) Food Consumption Patterns, 4) Agent Properties, 5} Agent Sources (including use patterns), 6) Environment Characterizations, 7) Environmental Agent Concentrations, 8) Food Contamination, 9) Physiological Parameters, 10) Risk Parameters, and 11) Miscellaneous Data Files. The Modeling Engine in THERdbASE has the following model groups: I) Population Distributions, 2) Location/Activity Patterns, 3) Food Consumption Patterns, 4) Agent Releases Characteristics, 5) Microenvironment Agent Concentrations, 6) Macroenvironment Agent Concentrations, 7) Exposure Patterns and Scenarios, 8) Dose Patterns, and 9) Risk Assessment. A list of the data related functions in THERdbASE is: «

* « * * * *

Data View for viewing contents of data files in tabular form; coded/decoded information can be viewed with a button click -columns of data can be set in "show" or "hide" mode; multiple data files can be viewed at the same time; data files can also be edited when in view mode. Data Query using simple query structures (filters) can be built on field values or on coded and decoded information. Statistics on the data fields: summary statistics (mean, std dev, min, max), percentile values at desired intervals, and linear regression on two numerical data fields. Graphics- model generated results can be viewed as: single/multiple bar, pie, line, and XY. Print- output to any printer: full contents of a data file, query results, graphs. Data Save/Export/Import- subsets of data files can be saved data can be exported to or imported from "dbf' format. Data Create- data files can be edited in advanced mode- new files can be created and information imported. The model related functions in THERdbASE are:

372


•

9

*

Data Input models are achieved through a standardized procedure as single values, custom distributions (normal, lognormal, etc.), distributions based on data files present in THERdbASE, or specific percentile values. Models have relational access to input data files, Model Execution uses efficient algorithms to access input data, to perform numerical simulations, to generate appropriate output data using a batch process. Data Output- output from models is done in the following two ways: as THERdbASE data files or as pre-set graphs.

Data files on the THERdbASE CD are: 1990 Bureau of Census Population Information, California Adult Activity Pattern Study (1987-88), AT&T-sponsored National Activity Pattern Study (1985), Chemical Agents from Sources, Chemical Agent Properties, Air Exchange Rates, Information from EPA's TEAM (Total Exposure Assessment Methodology) Studies, Information from EPA's NOPES (NonOccupational Pesticides Exposure Study) Studies, Information from EPA's AIRS (Aerometric Information Retrieval System), and Human Physiological Parameters. The models in the THERdbASE CD are: Chemical Source Release, Instantaneous Emission, Chemical Source Release, Timed Application, Indoor Air (2-Zone), Indoor Air (N-Zone), Exposure Patterns for Chemical Agents, Benzene Exposure Assessment Model (BEAM), Source Based Exposure Scenario (Inhalation + Dermal), and Film Thickness Based Dermal Dose. Minimum computer requirements to run THERdbASE are a 486 CPU, IBM or clone, at least 8 MB of RAM, at least 40 MB of disk space, color VGA monitor, a mouse, Microsoft Windows 3,1. To install THERdbASE, execute the File/Run option from within Windows and specify SETUP.EXE found in the THERDCD directory. This program leads you through the installation. Updates for THERdbASE can be obtained over the World Wide Web from the Harry Reid Center for Environmental Studies at the University of Nevada, Las Vegas (http://www.eeyore.lv-hrc. nevada.edu).

9.4 Summary This chapter concerned calculating the release and dispersion of hazardous materials. Section 9.1 discussed "hands-on" calculations to give the reader a better "feel" of the physics. In this, the hoop stress for the failure of tanks and pipes was presented, gas and liquid flow through a hole in a tank was calculated as were: UVCE (unconfined vapor cloud explosions), vessel rupture, BLEVE (boiling liquid expanding vapor explosion), and missiles. Atmospheric dispersion of chemical releases can be hand calculated using the Gaussian diffusion model but it was not discussed since it had been discussed previously (Section 8.3). While these basic methods are interesting, the modern approach to consequence calculations use computers. Section 9.2 summarized codes for release and dispersion, explosion and fire that were reviewed by the DOE APAC (Accident Phenomenology and Accident Assessment) program. Most of these codes are free and some can be downloaded over the Internet. Section 9.3 overviewed the EPA CD ROM entitled "Exposure Models Library and Integrated Model Evaluation Systems" which includes models for atmospheric, aquatic, point source, multiple source and multimedia models. It is likely that some of the information on this disk will be valuable to the reader. 373


Chapter 10 Assembling and Interpreting the PSA

10.1 Putting It Together At this point, following the chapters, the objectives have been defined, the effect of government regulations and standards are known, accidents have been identified and analyzed by various methods to determine the probability of an accident, and the accident consequences have been calculated. These parts must be assembled to present the risk and the analysis of the risk according to its various contributors.

10.1.1 Integrated and Special PSAs The scope and complexity of a PSA depends on its purpose. Large, expensive PSAs of a whole plant or group of plants (e.g., Canvey Island, Indian Point 2) are designated as integrated, meaning that the objective is the assessment of the overall accident" risk of a complex process. Integrated PSAs may be done to determine the financial exposure of a process as it is presently being conducted, or it may be in response to regulatory pressure. A special PSA is an accident risk analysis that is limited to a component, system, group of systems or a type of problem (e.g. DB-50 contactors, chlorine rail-loading facility, stress corrosion cracking, thermal shock, etc). We will address the problem of assembling an integrated PSA with the understanding that a special PSA is a subset of this and steps that are not needed for a smaller analysis may be excluded.

10.1.2 Assembling the PSA The assembly process (Figure 10-1) brings together all of the assessment tasks to provide the risk, its significance, how it was found, its sensitivity to uncertainties, confidence limits, and how it may be reduced by system improvements. Not all PSAs use fault trees and event trees. This is especially true of chemical PSAs that may rely on HAZOP or FMEA/FMECAs. Nevertheless the objectives are the same: accident identification, analysis and evaluation. Figure 10-1 assumes fault tree and event tree techniques which should be replaced by the equivalent methods that are used.

"There is little point in calculating the routine risk of an operating plant because it can be measured, however, there is good reason to calculated the routine risk of a plant before it is constructed or before restarting after major modifications to determine if the risk is tolerable. 375

Assembling and Interpreting the PSA Fault tree analysis

Event tree analysis

Accident analysis

Operation and function analysis and review Systems and interface irtterelationships (A)

4

* Failure definition and selection of top events

Containment failure modes

«

Containment analysis

V Fault tree construction | , Fault tree reduction

•—»f Containment event tree

i

J

Functional and system interrelationships Degraded core analysis

t Fault tree quantification

Radionuclide release and Accident sequence quantification

Dependent failure external events

Sequence category quantification

transport

Key sequence release category definition

identification of * common cause contributors * Identification of contributors needing detailed evaluation

Source term evaluation

Health economic effects

(to A)

Environmental analysis

Demographic characteristics

(Transportation evaluation

Fig, 10-1 PSA Assembly Process

Event Tree Development delineates the various accident sequences. This activity includes: an identification of initiating events and the systems that respond to each initiating event. Systems that serve to mitigate, but do not contribute to the prevention of a core melt accident, may be excluded, depending upon the purposes of the PSA. Separate event trees are generally constructed for each initiating event or class of initiating events having a unique event tree structure. System Analysis consists of five subtasks: 1) Link system event tree sequences to a containment event tree, 2) Eliminate unnecessary combinations, 3) Group remaining sequences by

376

Insights and Criticisms

release category, 4) Calculate sequence probabilities, and 5) Calculate release category frequencies. In the RSS method of PSA construction, a major task links system event trees with the for containment response. As illustrated in Figure 10-1 different end-points in the event tree may require different containment trees. It is also clear that the number of discrete sequences when the containment failure modes are considered can become quite large. This is treated in several ways. First, the end points in which the containment does not fail or fails by containment by-pass through the basemat are not considered further, because the offsite consequences are small compared with the consequences of containment. Also, end points of low relative probability and low consequences may be grouped with similar low-risk end points. Finally, the sequences must be grouped into release categories to reduce the number of consequence calculations to practicality. •

Analysis of External Events uses the models developed in the plant system analysis with considerations for seismic, fire, flood, high winds and missiles on the plant. Additional event trees or their equivalent may be needed for the external events.

»

Source Terms and In-Plant Transport the fraction of the inventory that makes it to the environment must be estimated. Computer models are to track the hazardous materials that are released from their process confinement through transport and deposition inside the plant to their release into the environment as a source term for atmospheric and aquatic dispersion.

•

Consequence Analysis the effects of the in the plant on the workers and the dispersed hazardous materials on the public and environment is assessed using computer models,

•

Uncertainty Analysis determines the effects on the overall results from uncertainties in the database, assumptions in modeling, and the completeness of the analysis. Sensitivity analyses determine the robustness of the results; importance calculations are useful for identifying and prioritizing plant improvements.

Assembling this material is a large data management task to assure the availability and traceability of all needed information with the output of one task fitting the input of another. This requires that quality assurance has been adhered to throughout the PSA project.

10.2 Insights and Criticisms Whether constructing a new PSA, modifying or using an old PSA it is worthwhile to ask what has been learned from previous works and some of the criticisms that have been levied against them. Fortunately the insights were largely supplied by NUREG-1050 from which the bulk of the following information is taken. The criticisms cover some of the same ground presented in Chapter 1 except with the bulk of PSA completed, the criticisms are more relevant.

377

Assembling and Interpreting the PSA

10.2.1 Insights from Past PSAs 1. 2.

3. 4. 5.

6.

7. 8.

The estimated probability of accidents leading to a hazardous release is higher than thought before PSAs were applied. PSAs estimate that the frequency of reactor damage cover about two orders of magnitude: from about lE-5/y to lE-3/y. This variation is attributable to: plant design, construction, and operation, to site characteristics, scope of the PSAs, and methods and analytical assumptions. Such comprehensive studies of comparable chemical process plants do not exist. For accidents to affect the public, containment and off-gas processing must fail, such as occurred at Bhopal and Chernobyl and did not occur at TMI-2. Plants meeting all applicable NRC regulatory requirements have been found to vary significantly in calculated risk and in terms of the key accident sequences. PSAs calculate that accidents more severe than those postulated in the design basis are the principal risk contributors. This indicates that safety designed with a specific goal is successful. Latent cancer is calculated to be the primary risk from a nuclear accident (this may be due to the conservatism in the low-dose models). At Chernobyl, most of the deaths were from fire and impact. Chemical process risk depends on the chemicals being processed. Experience shows that processing poisons poses the highest risk to public and workers. Most of the financial risk of a process accident is suffered by the plant, not by offsite property, although unemployment may be a major contributor to the financial loss. Demography has a large effect. At Bhopal, the surrounding population was dense, considering the hazardousness of the operation, and impeded emergency action.

10.2.2 Criticism of Past PSAs This section reflects on the limitations of the PSA process and draws extensively from NUREG-1050. These subjects are discussed as plant modeling and evaluation, data, human errors, accident processes, containment, fission product transport, consequence analysis, external events, and a perspective on the meaning of risk.

10.2.2,1 Completeness Nuclear PSAs tend to accept a set of initiators such as the WASH-1400 set or the EPRIset and proceed with little introspection as to completeness of the set for a specific plant. A well-known omission is sabotage. In general, earthquake and fire is treated poorly; tornado is usually not addressed nor are other aspects of adverse weather such as freezing and ice storms which may have common cause potential. The record has not been too good. After the Browns Ferry fire, it was claimed that such was addressed in WASH-1400. If so, attention was only brought after the fact. The TMI-2 sequence was not addressed in the PSAs to an extent that action was taken to prevent it.

378


10.2.2.2 Representativeness Representativeness can be examined from two aspects: statistical and deterministic. Any statistical test of representativeness is lacking because many histories are needed for statistical significance. In the absence of this, PSAs use statistical methods to synthesize data to represent the equipment, operation, and maintenance. How well this represents the plant being modeled is not known. Deterministic representativeness can be answered by full-scale tests on like equipment, Such is the responsibility of the NSSS vendor, but for economic reasons, recourse to simplified and scaled models is often necessary. System success criteria for a PSA may be taken from the FSAR which may have a conservative bias for licensing. Realism is more expensive than conservatism, Certainly errors should be conservative, but cumulative conservatism reduces accuracy and usefulness while raising costs. 10.2.2.3 Data Adequacy The nuclear equipment failure rate database has not changed markedly since the RSS and chemical process data contains information for non-chemical process equipment in a more benign environment. Uncertainty in the database results from the statistical sample, heterogeneity, incompleteness, and unrepresentative environment, operation, and maintenance. Some PSAs use extensive studies of plant-specific data to augment the generic database by Bayesian methods and others do not. No standard guidance is available for when to use which and the improvement in accuracy that is achieved thereby. Improvements in the database and in the treatment of data requires substantial industrial support but it is expensive. 10.2.2.4 Human Errors Human actions can initiate accident sequences or cause failures, or conversely rectify or mitigate an accident sequence once initiated. The current methodology lacks nuclear-plant-based data, an experience base for human factors probability density functions, and a knowledge of how this distribution changes under stress. The analysis of human actions is complicated because a human is a responsive system like a servo. Such analysis does not lend itself to simple models as do inanimate components. Classifying human actions into the success or failure states used in logic models for plant equipment does not account for the wide range of possible human actions. A generally applicable model of the parameters that affect human performance is not yet available. The uncertainties in human error rates may be within the stated uncertainty bounds, but such is not demonstrated from sparse experiments. Both the qualitative description of the human interaction logic and the quantitative assessment of those actions rely on the virtually untested judgment of experts.

379

Assembling ami Interpreting the PSA

10.2.2.5 Accident Analysis Nuclear PSAs contain considerable uncertainty associated with the physical and chemical processes involved in core degradation, movement of the molten core in the reactor vessel, on the containment floor, and the response of the containment to the stresses placed upon it. The current models of these processes need refinement and validation. Because the geometry is greatly changed by small perturbations after degradation has commenced, it is not clear that the phenomena can be treated. Full-scale core melt-water and core melt-concrete experiments are not feasible, but considerable progress has been made since the RSS in theoretical work, model development, and small-scale experiments using nonradioactive molten metal. There is increasing evidence that steam explosions in the reactor vessel and in the containment are incapable of failing the containment, There is still much to be done in characterizing the dispersal of the debris bed that may follow reactor vessel failure, the size of the corium particles formed, and the coolability of the resulting debris bed. 10.2.2.6 Containment Analysis Chemical process plants do not have a large domed containment but rely on vessel integrity and offgas processing. Most nuclear plants have such containment for which the stresses may be calculated if a scenario is defined. However such calculations are uncertain regarding the time of failure, the hole size, and location. Computer sensitivity studies show that hole size strongly affects the fraction of fission products released from the containment. The failure location determines mitigation due to release into another building in which condensation and paniculate removal occur. The quantity released depends on the time of containment fails relative to reactor vessel failure. If containment integrity is maintained for several hours after core melt, then natural and engineered mechanisms (e.g., deposition, condensation, and filtration) can significantly reduce the quantity and radioactivity of the aerosols released to the atmosphere. It has also been shown that heat radiation may heat and weaken the containment. The failure of penetration seals due to high temperature has been investigated, but full scale containment failure test have not been done. 10.2.2.7 Hazardous Material Transport Analysis Chapters 8 and 9 presented computer codes that are available for computer hazardous material release and transport. Many of these codes have been tested using controlled experiments with varying agreement depending upon the code's applicability to the phenomena. In the author's opinion, the accuracy of the consequence calculation is not much better than the calculation of accident probabilities.

380


10.2.2.8 External Events The methodology for assessment of external events is qualitatively satisfactory but not quantitatively. Little confidence should be placed in any estimates of the risk from external initiators compared to those from internal initiators. This is exacerbated by the fact that the external risk Is the larger of the two in many cases. 10.2.2.9 Risk The validity of the risk of nuclear that was estimated by the Reactor Safety Study was questioned when the TMI-2 accident occurred. This showed a misunderstanding of the probabilistic nature of risk. A single event neither proves nor disproves a statistical result; it may, however, question the usefulness of risk as a safety measure.

381


Chapter 11 Applications of PSA

11.1 U.S. Commercial Nuclear PSAs 11.1.1 Commercial Nuclear PSAs before IPE The primary motivation of PSAs is to assess the risk of the plant to the public. The immediate purpose of the RSS was to support the Price-Anderson hearings on liability insurance (i.e., assess the financial exposure of a nuclear power reactor operator) a purpose which, even today, is beyond PSA technology. However, PSA is sufficiently precise to provide relative risk comparisons of reactor designs and sites. These uses of PSA were presented at the Indian Point hearings, and in defense of Shoreham. The PSAs for the high-population-zone plants (Limerick, Zion, and Indian Point) were prepared to show that specific features of these plants compensate for the higher population density relative to plants studied in the RSS. The RSS was used by pro- and anti-nuclear power advocates in the Proposition 15 (nuclear power ban) voting in California; the Barsebek and Ringhals PSAs were prepared as part of the nuclear controversy in Sweden; the German Risk Study, 1981, had similar applications as did the Sizewell-B studies in Great Britain. After publication of WASH-1400, the Reactor Safety Study Methodology Applications Program (RSSMAP) was developed to extend PSA to other plants with other types of containment. RSSMAP addressed four plants: Oconee, a B&W PWR in a large dry containment; Calvert Cliffs, a CE PWR also in a large dry containment; Sequoyah, a W (Westinghouse, see Glossary) with an ice condenser containment; and Grand Gulf, a GE BWR in a Mark III containment. Following the TMI-2 accident and the endorsement of extended uses of PSA by the Kemeny Commission and the Rogovin Inquiry Group (Bernero, 1984), the Interim Reliability Evaluation Program (IREP) began with a study of Crystal River. This was followed by similar studies of four more plants (Table 11.1-1), These studies were limited to internal events leading to core melt with modest uncertainty and sensitivity analyses. The Accident Sequence Evaluation Program (ASEP) modeled 18 BWRs and 40 PWRs to represent the U.S. Nuclear Power Industry using a number of modules for different plant systems. The idea was to assemble fault trees of the modules that distinguish a plant and that this assembly will be the plant PSA. This work is largely unpublished, but NUREG/CR-3301 reports results at the system level. The NRC chose to test the methodology

383

Applications of PSA

Table 11.1-1 PSA Studies of U.S. Plants Completed before IPE Complete PSAs

Surry I (W)

Indian Point 2 & 3 (W) Yankee Rowe (W) Oconee 3 (B&W)

Clinch River Breeder Reactor (W)

Peach Bottom 2 (GE)

Big Rock Point (GE)

Zion 1 & 2 (W)

Limerick 1 & 2 (GE) Shoreham (GE)

Susque.han.na (GE)

Millstone 3 (W)

Millstone i (GE)

Oyster Creek (GE) McGuire 1 (W)

Sequoyah 1 (W)

Browns Ferry 1 (GE) Midland (B&W)

Seabrook (W)

Bellefonte (B & W)

TMI 1 (B&W)

Diablo Canyon (W)

Crystal River 3 (B&W)

IREPs or RSSMAPs

Oconee 3 (B & W)

Sequoyah 1 (W)

Grand Gulf 1 (GE)

Crystal River 3 (B & W)

Browns Ferry 1 (GE) Arkansas 1 (B & W) Millstone 1 (GE)

NUREG-1Q50

Peach Bottom 2 (GE)

Grand Gulf (GE)

Surry (W)

Catvert Cliffs (CE) Cal vert Cliffs 2 (CE) Sequoyah (W)

with in-depth PSAs, reported in NUREG-1150, with the technical bases in NUREG/CR-4550." Independently, the utilities owning Limerick, Zion, and Indian Point sponsored studies in response to the concern of the NRC regarding plants in high population zones. The Limerick PSA was performed by GE/SAIC in the style of RSS with alternative realistic analyses where justified. The Zion and Indian Point analyses (ZIP) were performed by one prime contractor (PL&G), using basically the same methods for all four plants. Other utilities have also contracted for and participated in the preparation of their own PSAs to estimate their public and financial risks, to obtain PSA-guided operational and safety improvements, and to provide technical rebuttals to NRC-ordered changes. In some cases, utilities have sponsored PSAs in response to local opposition to their license, e.g., Shoreham and Seabrook. Table 11.1-1 summarizes these PSAs,

11.1.2ATWS A long evolving use of PSA was for Anticipated Transients without Scram (ATWS) which extended over 15 years to culminate in NUREG-0460 which was upset by the Salem failure-to-scram incident and the subsequent SECY Letter 83-28. Other special studies have been: (a) value-impact analysis (VIA) studies of alternative containment concepts (e.g., vented containment, NUREG/CR-0165), (b) auxiliary feedwater studies, (c) analysis of DC power requirements, (d) station blackout (NUREG/CR-3220), and (e) precursors to potential core-damage accidents (NUREG/CR-2497), to name a few of the NRC sponsored studies.

11

Summaries of these results were reported in a special session of the American Nuclear Society ANS trans. 53, pp. 315-325, 1986.

384

U.S. Commercial Nuclear PSAs

Industry response is increasingly couched in PSA terms. In fact, the previously mentioned Big Rock Point PSA was not primarily to determine the public risk but to respond to post-TMI requirements. These were generic so that the low power of Big Rock Point in relation to the containment and unique design of this plant evoked a PSA-based utility response to show that the requirements applied to this plant could not be supported on the basis of a value-impact analysis (VIA). The PSA showed this conclusion and indicated areas of very effective improvements. Some other utility PSA responses have related to diesel surveillance testing, pipe rupture, sabotage, and hazardous gas releases near a plant. Many requests for technical specification (Tech Spec) changes are based on PSA.

11.1.3 Risk-Based Categorization of NRC Technical and Generic issues Perhaps the first well-known use of PSA insights in the regulatory process occurred in 1978 when the Probabilistic Analysis Staff performed a study (SECY/78-7516) to categorize the existing technical and generic issues facing the NRC. The primary objective was to assist in identifying, for action plans, those issues that have the greatest relative risk significance. One hundred thirty-three task action items were reviewed and assigned to four broad categories ranging from those having high-risk significance to those not directly relevant to risk. Of these, only 16 fell into the high-risk categories. The ranking aided the selection of the generic issues that would be designated "unresolved safety issues," This effort was redone by the NRC's Office of Nuclear Reactor Regulation (NRR) to include all TMI action plan issues and post-TMI issues. A most important product of a PSA is the framework of engineering logic generated in constructing the models. The patterns, ranges, and relative behaviors can be gained only from the integrated consistent approach PSA to develop insights into the design and operation of a plant. In reaching decisions, the regulator must compare the credibility of the information gained from PSA with the credibility of other sources of information. Thus, consider the magnitude of the estimated risk, the degree of uncertainty associated with it, the results of sensitivity analyses, and the net estimated effect of proposed alterations on the overall safety of the plant. Considered in this way, the PSA insights provide the decision maker with a comprehensive, contextual definition of the problem and a better quantitative understanding of the public risk with its uncertainties. The PSA objectively, instead of subjectively, judges aspects of risk.

11.1.4 Use of PSA in Decision Making The decision maker must weigh the qualitative and quantitative PSA insights and other information. There is no cookbook answer to this question, because it will depend heavily on the nature of the issue, the results of the PSA, the nature of other information, and other factors affecting overall judgment. The PSA should provide for the following needs: « * *

Scope and depth of the PSA should match the needs of the decision maker. Peer reviews should attest the credibility of the PSA results. Qualitative insights from the PSA should be plausible. 385

Applications of PSA

»

The effect of alternative regulatory actions on the estimated risk, including costs and impact.

11.1.5 Value-Impact Analysis (VIA) PSA techniques were used in the 1978 study of underground siting of nuclear power plants. NUREG/CR-0165, using insights from the RSS, considered nine alternative designs found to be the "logical alternatives." Filtered atmospheric venting was judged to be the most promising design alternative by value impact. This study contributed to the subsequent focusing of containment research on filtered vents and a diminution of interest in the underground siting of nuclear power plants. Other VIAs are the NRC-sponsored study of steam generators (Morehouse et al., 1983); three EPRI-sponsored VIA studies; a study of VIA applied to eight NUREG-0737 items specific to B WRs (NUREG-0626), Fullwood et al. (1984); a methodological development and application to shutdown heat removal, Fiksel et al. (1982); and a study of three auxiliary feedwater alternatives for PWRs, Stamatelatos et al. (1982).

11.1.6 Response to the TMI-2 Accident The NRC response to the TMI-2 accident (NUREG-0737) impacted the four U.S. LWR manufacturers. Consumers Power Company (a midwest utility) estimated that cost of retrofitting their Big Rock Point plant to be $125 million hence, not economical, given its age and size (240 MWt), nor were the requirements appropriate for unique characteristics of the plant and its siting. The utility initiated a PSA in which their plant personnel fully participated with the PSA contractors to identify and correct some areas of weakness. The NRC accepted the results without the major modifications that would otherwise have been needed. Furthermore, the understanding of the plant and its PSA by plant personnel made this a model for using PSA in plant improvement.

11.1.7 Special Studies 11.1.7.1 Analysis of DC Power Supply Requirements This study was undertaken as part of the NRC's generic safety task A-30, "Adequacy of Safety Related DC Power Supplies" (NUREG-0737). The issue stemmed from the dependence of decay-heat-removal systems on DC power supply systems. It was found that dc power-related accident sequences could represent a significant contribution to the total core-damage frequency. It was also found that this contribution could be substantially reduced by the implementation of design and procedural requirements, including the prohibition of certain design features and operational practices, augmentation of test and maintenance activities, and staggering test and maintenance activities to reduce human errors.

386


11.1.7.2 Station Blackout Two studies resolved the Unresolved Safety Issue A-44, "Station Blackout." The first study, "The Reliability of Emergency AC Power Systems in Nuclear Power Plants," when combined with the relevant loss-of-offsite-power frequency, provides estimates of station-blackout frequencies for 18 nuclear power plants and 10 generic designs. The study also identified the design and operational features most important to the reliability of AC power systems. The second study, "Station Blackout Accident Analysis" (NUREG/CR-3226), focused on the relative importance to risk of station-blackout events and the plant design and operational features that would reduce this risk.

11.1.7.3 Precursors to Potential Severe Core-Damage Accidents This study (NUREG/CR-2497) applies PSA techniques using operating experience to identify the high-risk features of plant design and operation. The operating experience base is derived from the licensee event reports (LERs) to find multiple events that, when coupled with postulated events, iead to plant conditions that could eventually result in severe core damage. In the first 2.5 years of the precursor study, 169 significant precursors were identified for the 432 reactor-years of operating experience represented by LERs submitted from 1969 to 1979; preliminary findings show 56 precursors for 126 reactor-years of operating experience for 1980-1981, The results were used to analyze accident sequences to estimate core melt frequencies for operating plants and to compare these results with the estimates in existing PSAs,

11.1.7,4 Pressurized Thermal Shock In addressing pressurized thermal shock, probabilistic assessments were used to derive screening criteria to identify operating plants needing modification. The owners' groups associated with the different PWR designs submitted estimates of frequencies of severe overcooling events. Analytical efforts using PSA techniques are exemplified in NUREG/CR-4183 and NUREG/CR-4022.

11.1.7.5 BWR Water Level-Inadequate Core Cooling PSA techniques were used in the analysis of TMI Action Item II.F.2, BWR water level inadequate core cooling. The results indicate that there is no need for additional instrumentation for detecting inadequate core cooling in the BWRs. The study showed that improvements in existing systems for water-level measurement and in operator performance (Shoreham and Limerick) could make the predicted core-damage frequency due to failure in water-level measurements in the plants analyzed much smaller than the total core-damage frequency predicted in recent PSAs for BWRs.

387

Applications of PSA

11:1,7.6 Other TMI Action Plan Items PSA provided tools for the analysis of TMI action items II .K.3.2 and II.K.3.17 (i.e., the frequencies of LOCAs caused by stuck-open pressurizer PORVs and outages of ECCS. respectively). The results of ILK.3.2 indicated that the frequency of small LOCAs from stuck-open PORVs was in the range of the small-LOCA frequency in the RSS and that no additional measures to reduce the PORV-LOCA frequency are required. The purpose of the data collection under item II.K.3.17 was to determine whether cumulative outage requirements are needed in the technical specifications and which plants had a significantly greater than average cumulative ECCS outage time.

11.1.7.7 LWR Shutdown Risk Usually, nuclear power plant PSAs are performed for what is thought to be the most dangerous operating condition: full power operation. The following, from Chu et al. (1995), analyzes the risk when a reactor is not only shutdown but the primary is opened and partially drained called mid-loop operation (MLO). Chu et al. found that the mean core damage frequency during MLO from internal events is about an order of magnitude less than during full power operation, for internal fire it is about twice that of power operation, and for internal floods it is about an order of magnitude less. In 1989, the NRC questioned the premise that most risk is in full power operation and requested an investigation of non-full power risk by BNL using Surry (two 788 MWe PWRs) as a model and SNL using Grand Gulf for a BWR model. NUREG-1150 results for the same plants in power operation was used for comparison. The investigation was Level 3 for internal events and Level 1 for internal fire, seismic, and flood induced core damage. Phase 1 identified vulnerable plant CDFs as high, medium, or low and provided core damage accident scenarios and risk information for a more detailed Phase 2 analysis in which MLOb was selected because it is the most hazardous shutdown condition. Phase 1, plant outages are: refueling, drained maintenance, non-drained maintenance with the residual heat removal (RHR) system, and non-drained maintenance without the RHR system. Plant operational states (POSs) were defined and characterized for each outage type. Each POS is characterized by a set of operating conditions (e.g., temperature, pressure, and configuration). For example, 15 POSs are used to represent a refueling outage. Each POS used Surry-specific data from reviewing operating and abnormal shutdown procedures, shift supervisor logs, monthly operating reports, and by performing thermal-hydraulic calculations (details are in Volumes 3 and 4 of NUREG/ CR-6144). Internal E¥ents The high risk POSs: R6, RIO, and D6 have different decay heats and plant configurations:

b

In MLO, the reactor is shutdown, and the coolant is drained until it is level with the center of the hot leg of the primary cooling system

388


• • •

R6, for eddy current testing of the steam generator tubes, is performed in a refueling outage by quickly draining the RCS loops, hence, the decay heat rate is high. R10, also in a refueling outage is for additional test and maintenance after some decay of the residual heat, D6 is MLO with the highest rate of decay: heat among the three mid-loop POSs.

Four time segments were defined for decay heat shutdown with unique sets of success criteria corresponding to the decay heat rate. R6 and D6 require all four time segments, but RIO only uses time segments 3 and 4. A statistical analysis determined the probability that an accident occurs in a particular time segment and an accident occurred. An event tree was developed for each initiating event, POS and time segment; 160 event trees were developed for 16 initiating events. Internal Fires The internal fire analysis is conventional. Surry-specific fire frequencies were assessed for important plant areas involving cable fires, transient fires, and equipment fires as a local phenomenon. The analysis locates the fire source and vulnerable equipment and/or cables. Cables of important systems were traced for vulnerability to a fire in various locations. Fire growth calculations (CQMPBRN-IIIe) were performed for the most vulnerable locations. A transitiondiagram type of suppression model was used, which, in conjunction with the fire growth model, gives the probability of damage given a fire in that location. The damage fraction with event tree and fault tree models gives the core damage frequency (CDF) for a fire scenario. The scenariodependent human error probabilities (HEPs) were estimated using the same human reliability analysis (HRA) method that was used in the internal event analysis. Fire Assumptions « Multiple initiators were not considered. » Fire barrier failure was not considered because of its small probability. « All cables were not traced if the risk they posed was small. • It was assumed fire frequency data from plants to Surry may be used. « Relay fires were screened probabilistically. • Both power and control cable were traced and considered. Internal Floods The internal flood analysis was conventional and consistent with the NUREG 1150 and IPE studies. The steps were: 1, 2,

Identification of Risk Susceptible Flood Areas was performed in the Phase t study using information from a plant visit and from NUREG-1150 and the IPE. Flood Event Frequency Estimates were developed from flooding events in nuclear power plants with adjustments for plant-specific features and data. The data were from the IPE Surry flood analysis, industry sources, and licensing event reports (LERs). Some plant specific models were developed for the circulating water (CW) and service water (SW) lines 389

Applications of PSA

in the Turbine Building whose flood dominates the risk. The dominant failure mechanism is large pipe rupture due to water hammer. Generic pipe failure data and Thomas (1981) were used when plant-specific data was unavailable. Flood barriers and other mitigators were considered in the damage states. The equipment damage due to internal flood is a function of flood level which depends on the flooding rate, confluence, drainage and mitigations. Flood damage states were developed to take these factors into account by incorporating the time dependency of the flood event and mitigations. The damage states represent a flood-exceedance frequency at a location with equipment damage criteria. The flood initiating frequencies were developed to incorporate simple recovery actions as expected from experience.

Location and Scenario Identification Potential accident scenarios and flood locations were identified from plant drawings and the RHR system fault tree that identifies the equipment and support needed for RHR system operation. The equipment location was correlated with flood areas with consideration for plant features which may impede or divert the flow. The flood scenarios identify the effect on systems required to prevent core damage. Quantification accounts for the rate of rise of the flood relative to the critical level in each specific plant area. The time available for any recovery action is calculated from the volume and the flow rate. Table 11.1-2 Shutdown CDF (Mid-Loop Operation) and Full Power CDF

Results Study Mean 5th% 50th% 95th% Error Table 11.1-2 preInternal Full Power NUREG-1 150/y 4.0E-5 6.8E-6 2.3E-5 3.3E-4 4.4 sents the CDFs of different Events Full Power IPE/y 7.4E-5 events in MLO, summarizes 4.9E-6 4.8E-7 2.1E-6 1 .3E-5 5.7 MLO/y (while in MLO) results, and compares them Internal Full Power NUREG-1 150/y 1.1E-5 with NUREG-1150 and IPE Fires results for the same plants. MLO/y (while in MLO) 2.2E-5 1 .4E-6 9.1E-6 7.6E-5 7.2 Also, presented are the Internal Full Power IPE/y 5.0E-5 Flood level-1 uncertainty analysis, MLO/y (while in MLO) 4.8E-6 2.2E-7 1 .7E-6 18E-5 9.0 results. The MLO mean LLNL 1.2E-4 Seismic Full Power 33 core damage frequency Events NUREG-1 150/y EPRI 4.0E-5 4.4 from internal events is MLO/y (while in LLNL 3.5E-7 32 about an order of magnitude MLO) 37 8.6E-7 EPRI lower than that of full power operation. The mean core damage frequency due to internal fire is comparable to that of power operation. Like internal events, the mean core damage frequency due to internal floods is comparable to that of power operation as estimated by IPE,

390


Insights Internal Event and Operator Response in MLO - dominated CDF because of operator failure to mitigate the accident with a very large uncertainty. Procedures for Shutdown Accidents - there are few procedures for accidents in MLO, Procedure for loss of decay heat removal, AP 27.00, is the only one written specifically for the shutdown scenarios analyzed in this study. The procedure is conservative regarding equipment needed to establish reflux cooling and feed-and-bleed. This study treated fewer than the number of steam generators specified in the procedure for reflux cooling as a recovery action with more realistic success criteria for feed-and-bleed with high decay heat. Some procedures are wrong for MLO conditions, e.g., procedure for loss of offsite power, AP 10.00, states that when the EDO is the only source of power, the Component Cooling Pump should not be in service. During shutdown, CCW flow to the RHR heat exchanger is necessary for decay heat removal. Instrumentation: level instrumentation for MLO (standpipe level and ultrasonic) has limited use in a shutdown accident. Standpipe level is correct in the absence pressure in the system, Ultra-sonic is correct only when the level is within the reactor coolant loops. Thermal-Hydraulic Analysis must be extended to at least 24 hours into the accident. This study used calculations for feed-and-bleed operation with a charging pump, and with gravity feed from the refueling water storage tank (RWST). Maintenance Unavailability; shift supervisor's logs and minimum equipment lists so unavailability of equipment needed to mitigate a shut-down accident. Isolation of Reactor Coolant Loops - contributes to the core damage frequency by being isolated in a refueling outage to disable the affected steam generators for decay heat removal upon loss of RHR. In a cold shutdown, the steam generators are maintained in a wet lay-up condition with the secondary side filled with water. During mid-loop operation, reflux cooling with the steam generators is a possible mitigation for loss of RHR especially in a station blackout. Valve Arrangement of Auxiliary Feedwater System and Main Steam System during Shutdown - the auxiliary feedwater system has six MOVs in the flow path to the steam generators and the main steam nonreturn valves are normally closed during shutdown. These valves depend on offsite power and are difficult to manually open. Potential for Plugging the Containment Sump When Recirculation Is Needed: transient material and equipment are brought into containment during shutdown. This could increase the potential for plugging the containment sump if an accident requiring recirculation from the containment sump occurs. Internal Fire CDF is less likely during shutdown than under power but welding or cable fires may be more likely. A fire at shutdown may be detected and extinguished more readily because of floor traffic. However cable routing to support RHR or to mitigate an accident during mid-loop operation can result in fire critical intersections. Risk significant scenarios involved in the emergency switchgear room (ESGR), the cable vault and tunnel (CVT), and the containment. In the ESGR, the most risk significant ESGR scenarios occur in locations where many cables for the H and the J emergency divisions come together in close proximity. The tunnel part of the CVT is a constrained space, where damage would quickly propagate to both divisions. In containment, the risk is from the relatively high fire frequency and non-separation of the two RHR divisions.

391

Applications of PSA

Internal Flood is dominated by Turbine Building flood events which may be initiated by valve or expansion joint failures in the main inlet lines of the circulating water system. At Surry the circulating water system is gravity fed from a large capacity intake canal and isolation is not quick and cannot be accomplished in a timely manner. At other plants, stopping dedicated cooling water pumps would stop the flood. The potential draining of the intake canal into the Turbine Building is a dominant risk because of the spatial interdependence of this plant. For both units, the Emergency Switchgear Rooms are located in the Service Building on the same elevation as the Turbine Building basement, but separated by a fire door and 2 foot flood dikes. A large flood could overflow the dikes, and the two-unit ESGR to lose emergency power for both units. Normal off-site power to the plant would not be affected since the normal switch gear room is at a higher elevation.

11.1.8 Individual Plant Evaluation PSAs 11.1.8.1 Overview On August 8,1985, the U.S. Nuclear Regulatory Commission (NRC)C requested the operators of nuclear power plants in the U.S. to perform Individual Plant Examinations (IPE) on their plants. IPEs are probabilistic analyses that estimate the core damage frequency (CDF) and containment performance for accidents initiated by internal events (including internal flooding, but excluding internal fire). Generic Letter (GL) 88-20 was issued to implement the IPE request to "identify any plant-specific vulnerabilities to severe accidents and report the results to the Commission." 75 IPEs for 108 plants (Table 11.1-3) were prepared by licensees and/or consultants in varying depth and methodology. They were reviewed by the NRC Office of Nuclear Regulatory Research (NUREG-1560) regarding four major areas: 1. 2. 3. 4.

Risk of U.S. nuclear power, Plant improvements indicated by their IPE, Plant-specific features and modeling assumptions affecting risk, and Use of IPEs for risk-based regulation.

Core damage and containment performance was assessed for: accident sequences, component failure, human error, and containment failure modes relative to the design and operational characteristics of the various reactor and containment types. The IPEs were compared to standards for quality probabilistic risk assessment. Methods, data, boundary conditions, and assumptions are considered to understand the differences and similarities observed.

c

"Policy Statement on Severe Accidents Regarding Future Designs and Existing Plants" (Federal Register, 50FR32138). 392


Table 11.1-3 IPE Submittals (BWR is GE, B&W is Babcock & Wilcox, CE is Combustion Engineering, and W is Westinghouse) Big Rock Point; Dresden 2,3; Millstone 1; Oyster Creek; Nine Mile Point 1 BWR 1/2/3

BWR 3/4

These piants generally have separate shutdown cooling and containment spray systems and a multi-loop core spray system. With the exception of Big Rock Point, which is housed in a large dry containment, these plants use an isolation condenser Browns Ferry 2; Brunswick 1,2; Fermi 2; Fitzpatrick; Limerick 1 ,2; Monticello; Quad Cities 3, 2; Susquehanna 1, 2; Cooper; Duane Arnold; Hatch 1. 2; Hope Creek; Peach Bottom 2, 3; Pilgrim !;• Vermont Yankee These plants are designed with two independent high-pressure injection systems, namely reactor core isolation cooling and high-pressure coolant injection (HPCI). The associated pumps are each powered by a steam-driven turbine. These plants also have a multi-loop core spray system and a multi-mode residual heat removal (RHR) system that can be aligned for low-pressure coolant injection, shutdown cooling, suppression pool cooling, and containment spray functions. Clinton; Grand Gulf 1; Perry 1; River Bend; LaSalle 1,2; WNP 2; Nine Mile Point 2

BWR These plants use a high-pressure core spray (HPCS) system that replaced the HPCI system. The HPCS system 5/6 consists of a single motor-driven pump train powered by its own electrical division complete with a designated diesel generator. These plants also have a single train low-pressure core spray system, as well as a multi-mode RHR system similar to the system design in the BWR 3/4 group. ANO 1; Crystal River 3; Davis Besse; Oconee 1, 2 & 3; TMI 1 B&W The B&W plants use once-through steam generators. Primary system feed-and-bleed cooling can be established through the pressurizer power relief valves using the high-pressure injection (HPI) system. The HPI pump shutoff head is greater than the pressurizer safety relief valve setpoint. Emergency core cooling recirculation (ECCR) requires manual alignment to the containment sumps. The reactor coolant pumps (RCPs) are generally a Byron Jackson design. ANO 2; Calvert Cliffs 1,2; Fort Calhoun 1; Maine Yankee; Millstone 2; Palisades; Palo Verde 1 , 2 , 3 ; CE San Onofre 2, 3; St. Lucie I, 2; Waterford 3 The CE plants use U-tube steam generators with mixed capability to establish feed-and-bleed cooling.! Several CE plants are designed without pressurizer power-operated valves. The RCPs are a Byron I Jackson design. West nghouse Ginna ; Kewaunee;- Point Beach 1, 2; Prairie Island 1, 2 W 2-loop These plants use U-tube steam generators and are designed with air-operated pressurizer relief valves. Two independent sources of high-pressure cooling are available to the RCP seals. Decay heat can be removed from the primary system using feed-and-bleed cooling. ECCR requires manual switchover 1 to the containment sumps. The RCPs are a Westinghouse design. W Beaver Valley 1, 2; Farley 1, 2; North Anna 1, 2; Robinson 2; Shearon Harris 1; Summer; Surry !, 2; 3-loop Turkey Point 3,4 This group is similar in design to the Westinghouse 2-loop group. The RCPs are a Westinghouse design. W Braidwood 1, 2; Byron 1,2; Callaway; Catawba 1, 2; Comanche Peak 1, 2; DC Cook 1,2; Diablo Canyon 1.2; 4-loop Haddam Neck; Indian Point 2, 3; McGuire 1,2; Millstone 3; Salem 1,2; Seabrook; Sequoyah 1, 2: South Texas 1, 2; Vogtle 1,2; Watts Bar 1; Wolf Creek; Zion 1,2 The Westinghouse 4 1 oop group includes nine plants housed within ice condenser containments. Many of these plants have large refueling water storage tanks such that switchover to ECCR either is not needed during the assumed mission time or is significantly delayed. The RCPs are a Westinghouse design.

393

Applications of PSA

11.1,8.2 Impact of the IPE Program on Reactor Safety The primary licensee goal was to: "identify plant-specific vulnerabilities to severe accidents" that could be reduced with low-cost improvements. However, GL 88-20 did not define what constitutes a vulnerability; hence, the IPEs are diverse in the vulnerability criteria, hence, a problem considered to be a vulnerability at one plant may not be identified as a vulnerability at another plant. Less than half of the licensees identified "vulnerabilities" in their IPE submittal; but nearly all of the licensees identified areas warranting investigation for potential improvements. Thus, the IPE program provided impetus for improving the overall safety of nuclear power plants. Four boiling water reactor (BWR), and 15 pressurized water reactor (PWR) licensees acknowledged plant vulnerabilities. Some BWR vulnerabilities are failure of: • • • •

Water supply to isolation condensers High-pressure coolant injection and reactor core isolation cooling when residual heat removal has failed Control of low-pressure injection during an anticipated transient without scram (ATWS) Dry well steel shell to prevent melt-through in a Mark I containment Some PWR vulnerabilities are:

• « « • • • • • • •

Reactor coolant pump (RCP) seal failures that lead to a loss of coolant accident (LOGA) Turbine-driven auxiliary feedwater pump reliability-from design and maintenance problems Internal flooding caused by component failures Operator failure to switch over from the coolant injection phase to the recirculation phase Critical switchgear ventilation equipment failure leading to loss of emergency buses Operator failure to depressurize during steam generator tube rupture Valve surveillance that leads to interfacing system LOCAs Loss of certain electrical buses Compressed air system failures Inability to crosstie buses during loss of power

Most than 500 plant design or operation improvements were identified by licensees: 45% of the improvements were procedural/operational changes; 40% were design/hardware changes. Few of the improvements change maintenance. Procedural or design changes require training revision. Approximately 45% of the plant improvements had been implemented; 25% had been implemented and were credited in the IPEs. Other improvements were planned or under evaluation. Utility activities and other requirements (primarily the station blackout rule) are reasons for change. While these changes may not be due to the IPE, the IPE prioritizes the implementation. Specific improvements vary with plants, but common improvements were: changes to AC and DC power, coolant injection systems, decay heat removal systems, heating ventilation and air conditioning systems, and PWR reactor coolant pump seals.

394


11.1.8.3 IPE Core Damage Frequency Assessment IPE results genrally are consistent with the results of previous NRC and industry risk studies in indicating that the CDF is often determined by many accident sequence combinations, rather than a failure. The largest contributors to CDF vary among the plants (e.g., LOCAs dominate some IPE while station blackout [SBO] dominates others). Support systems, whose design varies considerably with plant, are important to all plants because they can cause multiple front-line system failures. This may account for much of the variability in the IPE results. Consistent with previous risk studies, the average CDFs reported for BWRs is less than for PWR as shown in Figure 11.1-1. BWR and PWR results are strongly affected by the support system considerations discussed above, but some differences between the two types of plants explain why the average is less for BWRs: *

* * *

'A

AA

5 1E-5 AAA

A

PWR A

A,

BWRs have more injection systems than PWRs and can BWR depressurize more easily using low-pressure injection (LPI) Fig. 11.1.-I Summary of systems which reduces the BWR LOCA vulnerability. Figure BWR and PWR CDFs from 11.1-1 shows some BWR CDFs are higher than some PWR IPEs CDFs The variation in the CDFs is driven primarily by a combination of the following factors: Plant design differences (primarily in support systems such as cooling water, electrical power, ventilation, and air systems) Variability in modeling (e.g., accounting for alternative accident mitigating systems) Differences in data used in quantifying the models .1

t08

11.1,8.4 Containment Performance

I

IPE accident progression analyses generally are consistent with typical analyses of containment performance. Failure mechanisms identified in the past as important are important in the IPEs. In general, the IPEs confirmed that the larger volume PWR containments are more robust than the smaller BWR pressure suppression containments in meeting the challenges of severe accidents (Table 11.1-4). Containment performance is important to reducing the risk from early releases. Analyses in IPE submittals emphasize phenomena, mechanisms, and accident scenarios associated with early

395

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1°^ s .

306
20 miles from an airport, not on an airway and built with blast resistant construction. The nearest public highway is 2 miles away, the nearest pipeline 17 miles away, the nearest public

420

Research and Production Reactor PSAs

railway is 2.8 miles away and there is no ship traffic on the Savannah River. A study of the risks from onsite transportation of hazardous substances postulated that any release would cause control room evacuation. These also were evaluated to be negligible. Another possibility is dropping into the heat exchanger bay the 100 ton heat exchanger to cause a primary or secondary LOCA. If irradiated fuel were still in the reactor, melting could occur. Heat exchangers have been removed with hot fuel in the Table 11.3-6 Point Estimate CDFxfor the reactor (at least twice since 1971). This scenario .was K-Reactor estimated to be ~ lE-4/y and procedures were changed Class of Accident Init. /y CDF/y % to eliminate it. Primary LOCA 5.6E-3 1.2E-4 59

11.3.4.4 Results

Secondary LOCA

3.3E-3 4.9E-5

Transients

2.5

24

1.6E-5 8

Loss of River Water 1.2E-3 l.OE-5 5 The point estimate core damage frequencies for 1.2E-4 9.8E-6 4 Loss of Heat Sink the K-Reactor for both internal and external initiators 2.1E-4 100 Total Internal Events are given in Table 11.3-6. Seismic 1.2E-4 Internal accidents, alone, have 267 sequences Crane Failure
421

Applications of PSA

header failures (-2 psi) and collapse from steam condensation. The PSA

The PSA (Miller, 1990, Wyss, 1990a, 1990b) consisted of three steps: 1) issues important to safety were identified by "brainstorms" constructed as an accident progression event tree, 2) deterministic calculations were performed on the issues when information was not available from previous calculations or similar systems, and 3) information from step 2 was used to elicit expert judgement of the issues identified in step 1. Its unique design suggests several accident scenarios that could not occur at other reactors. For example, failure to supply ECC to 1/16 of the core due to the failure of an ECC inlet valve. On the other hand, some phenomena of concern to other types of reactors seem impossible (e.g., core-concrete interactions). The list of phenomena for consideration came from previous studies, comments of an external review group and from literature review. From this, came the issues selected for the accident progression event tree (APET) according to uncertainty and point estimates. 423

Applications of PSA.

A issue addressed was the hydrogen generation rates and the possibility of a hydrogen explosion and the small building failure pressure. Another issue was the amount of fuel damage that could occur during degraded emergency cooling which could occur: from complete loss of the ECCS, by ECCS valving that blocked a single riser, or by common cause failure of the inlet riser valves or the emergency dump tank valves. These complexities in the primary system thermal- hydraulics make uncertainties in estimating fuel damage. N-Reactor features raised accident progression questions such as the "banana" that divides the zone I confinement from a zone III confinement area (zone I is the reactor building, zone III is a lower level of confinement). A lower portion of this wall extends into a pool of water where the underwater conveyor belt moves spent fuel from the reactor to the examination and storage facility. Is possible that during confinement pressurization, the water level on the zone I side of the wall may be depressed enough to allow gas venting under the wall. Such issues were analyzed according to availability of information and importance of the phenomena to the overall results. Accident Calculations

Calculations of fuel damage used integrated severe accident code developed at SNL, MELCOR with a new core package to specifically model the N-Reactor. MELCOR allowed modeling of a complete accident scenario from initiating event to the radionuclide release (if any) from the confinement. In particular was the fairly high likelihood T4 transient sequence involving the failure-to-open of 1 of 2 check valves in the emergency core cooling system. The MELCOR calculation assumed that the primary coolant pumps and reactor were tripped at time zero and the ECCS valves opened within 67 seconds (based on RELAP5). The ECCS functioned normally except for flow to the highest power density fuel. Another complex problem is how much fuel can fail if only a portion of the ECC is supplied. This was addressed by an upper bound calculations using RELAP5 and engineering judgment. The detailed calculations showed that peak temperatures did not occur during the blowdown because water flashed to steam but in the reflood stage of the accident. Reflood of the upper core levels took longer than reflood of the lower levels, the pressure drop in the reflooded portions continually decreased as the fraction reflooded increased, and the lower pressure drop yielded lower forces to drive the reflood process for the remaining tubes. From this it appears that fuel heat up during the blowdown phase would not fail in any fuel. During the reflood phase, the ECC will initially be reflooding a relatively small portion of the core with a high water flow rate with a high pressure drop across the core that will drive a large steam flow through the upper, unflooded regions. However, as more of the core is flooded the pressure differential will become lower, thus driving a smaller steam flow through the unflooded regions which may not prevent fuel damage. The maximum level of reflood that would provide an adequate pressure differential for steam cooling of the remaining unflooded region was calculated with MELCOR to find the maximum fuel temperature and pressure drop for steam-filled tubes for varying steam flow rates, and to characterize the pressure drop that develops in reflooded tubes for varying levels of ECC flow per tube. Combining the information from these relatively simple calculations, determines an upper bound estimate for a given fuel failure temperature and ECC flow rate.

424


Hydrogen production, transport and explosion was addressed with MELCOR Version 1.8.0 and HECTR 1.5N. HECTR 1.5 is a lumped-parameter containment analysis code for calculating containment atmosphere pressure temperature response to combustion. HECTR 1.5N is a modification of this code for the N-Reactor where a major concerns is the possibility of a hydrogen explosion during an accident in a building only capable of 5 psi. The hydrogen production was calculated according to the ECCS and GSCS cooling available in the first 2 hours and in the first 24 hours. Irs 5 calculations with the same basic set of assumptions, hydrogen production was maximized by conservatively assuming an unlimited steam supply for oxidation that did not cool the fuel The possibility of pressure relief through the banana wall was addressed with several MELCOR calculations assuming instantaneous confinement pressurizations of: 4, 4.5, 5, and 6 psi, a small LOCA, and nitrogen injection from the hydrogen mitigation system. These calculations showed the response of the banana wall to various confinement pressurizations. Expert judgement was used to estimate uncertainty distributions for the parameters using the issue definitions with the accident calculations. Expert judgement elicitation used the method of NUREG/CR-4550. Independent panels were not convened; the panels consisted of project members and experts familiar with N Reactor, but the fundamental structure of NUREG/CR-4550 was retained (i.e., elicitation training and debiasing of the experts, issue decomposition, aggregation of independent elicitations). Typically, participants were asked to consider an issue or parameter. Each analyst established his realistic bounds for the parameter's value. Then, a cumulative probability function (CPF) for the parameter was developed. This might be a well defined probability distribution with mean, standard deviation, and shaping factors, or it might be an empirical CPF characterized by parameters for probability quartiles. The elicitations from analysts were weighted equally and 2 or 3 individual distributions were arithmetically averaged to yield an aggregated CDF for the parameter. Event Trees and Fault Trees An accident progression event tree (APET) (Wyss, 1990) modeled the primary and confinement system responses to the accidents found in the Level I analysis. It consisted of 87 events to model the core damage state, confinement venting, and isolation status. The accident progression phenomenology includes hydrogen and graphite issues, filter effectiveness, pressure suppression, and the formation of air and liquid pathways for the release of radionuclides from the plant. The APET results were generated by the EVNTRE code and analyzed by a parametric source term model (NSOR) to determine the radioactive source term for each accident progression pathway found in the APET analysis. These source terms were then grouped and analyzed for consequences using MACCS. The risk-results were finally calculated by PRAMIS. These codes (or, in the case of NSOR, types of codes) were used in NUREG-1150 as well as Latin Hypercube Sampling (LHS) and Monte Carlo uncertainty analysis techniques to produce an integrated uncertainty analysis for the entire PSA. Results The mean frequencies of events damaging more than 5% of the reactor core per year were found to be: Internal Events: 6.7E-5, Fire: 1.7E-5, Seismic: 1.7E-4, and total: 2.5E-4. Thus, within the range of U. S. commercial light water reactors The core damage frequency itself, is only part of the story because many N-Reactor accident sequences damage only a small fraction of the core. The

425

Applications of PSA

pressure tube design makes it possible to lose emergency cooling to parts of the core while successfully cooling the remainder. In addition, the GSCS is shown to provide sufficient cooling to prevent fuel damage in large regions of the core. Thus, the PRA showed that more than 95% of all internal core damage accidents involve failure of less than half of the fuel in the reactor. This significantly reduces the radionuclide inventory for release for further reduction by the confinement systems. The uniqueness of the N-Reactor results in sparse data questionable applicability of generic failure data. A key insight is active systems can inadvertently interfere with passive systems unless precautions are taken. The accident progression analysis showed; «

•

« * «

The confinement maintains its integrity in more than 85% of internally initiated core damage accidents. About half of these failures are from mispositioning of a single switch to fail both the ECCS and confinement isolation. About half of the confinement failures are caused by hydrogen combustion in an ECCS effluent dump tank. Inerting the atmosphere in this tank would further reduce the confinement failure rate. The gaseous effluent filtration system was found to operate successfully in 95% of the internally initiated core damage accidents in which the confinement maintains its integrity. A fire in either of two critical areas would disable all front line and emergency core cooling systems, but not affect confinement isolation and effluent filtration. A seismic event three times or more the 0.25 g safe shutdown earthquake was the only significant mechanism found to cause oxidation of the graphite moderator stack.

The inventory of long-lived fission products is far less than an LWR because of the short exposure of the fuel to minimize Pu-240 production. But the health effects from an accident are comparable because it primarily results from short lived radionuclides. N Reactor accidents are expected at lower fuel temperatures than LWR accidents. The large thermal capacity of the graphite moderator stack, the low melting point of the fuel (1,407°K) and the GSCS contribute to lower accident temperatures which retains heavy metals in the fuel. The public consequences were significantly lower public than expected for a typical commercial LWR primarily because of the large distance to the public (>6 miles) and dispersal afforded by the height of the stack. The mean frequencies per year for offsite early fatalities are Internal Events: 9.7E-13, Fire: 3.8E-9, Seismic: 2.2E-8, and Total: 3.1E-9. For offsite latent cancer fatalities the results are: Internal Events - 4.1E-3, Fire - 4.2E-3, Seismic - 6.0E-2, Total - 6.8E-2. For onsite early fatalities the results are Internal Events: l.OE-6, Fire: 8.3E-5, Seismic: 8.6E-4, and Total: 9.4E-4. For onsite latent cancer fatalities the results are Internal Events: 2.7E-4, Fire: 2.3E-4, Seismic: 3.0E-3, and Total: 3.5E-3.

11.3.6 Omega West Reactor PSA The Omega West Reactor (OWR) is a water-cooled pool reactor operated by for the DOE by Los Alamos National Laboratory (LANL) for neutron irradiation experiments at a power of 8 MWt 426


about 40 hrs per week. It is cooled by water at 40°C, atmospheric pressure flowing at 3500 gpm. It is powered by 33 fuel elements of the Materials Testing Reactor (MTR) type. These elements tested at the MTR such that 31 fuel elements operated at 30 MWt. Thus Omega West operates at 21% of the power at which the fuel has been tested. A simple Level 1 PRA was prepared by Idaho State University College of Engineering (Neill, 1990a, Neill, 1990b) commensurate with the simplicity of OWR. Gradations of fuel damage were not defined. Accident scenarios were evaluated according to: the probability of fuel element damage or the probability of shutdown without fuel element damage. Operators were assumed not to scram in response to instrument readings. Nevertheless, the results of binary consequences is useful for establishing the relative probability of accidents covered by protective systems to those not covered. Initiating Events The OWR facility procedures, schematics, systems inspections, and staff interviews were studied including after which a Master Logic Diagram (MLD) constructed that identified 24 independent, generic for fuel damage events. Of these, 12 were sequential in that installed protective systems could intervene and prevent fuel element damage by shutdown or emergency cooling. The remaining 12 events were treated as leading directly to fuel element damage. The initiating event probabilities were quantified, using chi-squared estimation with one degree of freedom (no failures) to estimate the mean time between occurrences at 50 and 95 percentile confidence levels for initiating events over 30 years (15.6 and 132 years respectively). The mean time between occurrences were inverted to yield aggregate failure frequencies which were prorated equally over all 24 generic initiating events for frequencies at the 50% and 95% confidence levels. A log-normal probability density was assumed for the distribution of the individual initiating event frequency and a mean value and error factor were calculated. This substitution of log-normal distribution for chi-squares was a computational simplification. A Poisson probability distribution was assumed for the number of initiating events occurring over a one-year mission time. Each initiating event probability is generic in that it describes a group of failures that lead to a particular event without specifying any details of the failure. The MLD showed that all protective systems were challenged by either 1, 2, 3. or 5 initiating events. Event and Fault Trees The OWR protective systems were modeled with event tree diagrams for the time sequence following an initiating event to fuel damage or safe shutdown. Fault trees were used to find the probability of failure of each protective system in a particular event tree. Results Three steps were involved: 1) protective system fault tree top event probabilities were calculated by the IRRAS2 computer code; 2) probabilities applicable to a given event tree were combined with the initiating event probability, to give the probability of a fuel damage state or safe shutdown; 3) fuel damage probabilities from all event trees were combined for the total probability of fuel damage from the protected sequences. The probabilities of fuel damage according to initiating

427

Applications of PSA 10

event type is shown as probability densityJ functions in Figure 11.3-1.

| 0.9 h

°

;

Reactor Period (1)

0.8 '

11.4

Chemical Process

PSAS

„, Q

ft

HighCodant

I 0.8 | -

-'

Temperature^}

!

if o.s r -

•

#

r i i i L • i 1 Low Coolant Unfortunately chemical 1 0 4 ;' Neutron Level " (1)* FIOWCT process plant PSA have no J: [ requirements for public disclosure, ', LOCA(5> ' consequently examples of their PSAs * * Tola! 01 are hard to find. However the following are some examples from 0-01E;10 1E;9" 1E;8 ;E.7 ~1E.6 1E.5 î.4 ~ 1E.3 Fuel the open literature. They are similar Damage Frequency iy

to nuclear PSAs except less elaborate FiS- l L3~* Omega West Results (Numbers in parenthesis are number with more empahsis on consequences of initiating events) than on probabilities. In addition to these are studies prepared before President Carter stopped the GESMO (Generic Environmental Statement for Mixed Oxide) that addressed the chemical processing of fissionable material for the nuclear fuel cycle. Some references are Cohen (1975), Schneider (1982), Erdmann (1979), Fullwood (1980), and Fullwood (1983).

11.4.1 Canvey Island 11.4.1,1 Background The Site Canvey (1978) is a study of the risks of a petrochemical complex that already involved plants operated by Shell UK Oil, Mobil Oil Co. Ltd., Calor Gas Ltd., United Refineries, Occidental Refineries Ltd., Texico Ltd., and British Gas Corporation. In March 1976 the Health and Safety Commission agreed to a request to investigate the risks to health and safety associated with various installations, both existing and proposed, on Canvey Island and the neighboring part of Thurrock (Figure 11.4-1). The investigation followed an exploratory public inquiry recommending revoking the permission given in 1973 to United Refineries Limited to build an oil refinery on Canvey Island. This report recommended a detailed risk study because of the exceptional concentration of hazards and the demography. The investigating team consisted of personnel of the Safety and Reliability Directorate of the U.K. Atomic Energy Authority with expertise in hazard evaluation, the District Inspector of Factories for South Essex, and a Senior Chemical Inspector of Factories. The investigating team was charged to realistically assess the risk at individual installations before considering interactions that may arise from fires, explosions and the release of airborne toxic substances and other interactions between installations.

428

Chemical Process PSAs

The area is about 9 miles from west to east, along the north bank of the Thames, and 2.5 miles north to south at its widest, across Canvey Island. The area is divided by Holehaven Creek which separates Canvey Island from the mainland of Thurrock to the west. It is flat, low-lying salt marshland protected by sea walls. Canvey Island was reclaimed from the sea in the early 17th century. The population is about 33,000. New housing is being built and older property is steadily being replaced. Figure 11.4-1 shows the residential areas on the eastern half of the island, light industrial development is towards the southwest. Texaco Limited and London and Coastal Oil Wharves Limited tank storage, and the British Gas Corporation methane terminal front on the Thames. Occidental Refineries Limited and United Refineries Limited have requested permits to construct oil refineries on the west side of the island (at the time of the report's publication). The part of the mainland within the area covered by the investigation is not residential, but primarily industrial. The two large oil refineries belonging to Shell UK Oil and Mobil Oil Company Limited are located on the riverside. The liquefied petroleum gases cylinder (LPG) filling plant of Calor Gas Limited is north of the refineries. Fisons Limited's ammonium nitrate plant is in the western part of the area. Manor Way, A1014 provides road access to the mainland; a rail line for freight runs from the main line through the Shell UK Oil refinery to Thames Haven, and to the Mobil Oil distribution terminal at Coryton, A deep water channel provides access to the ten jetties of the two refineries. The control room and pumping station for the U.K. oil pipeline is located at Coryton. Oil products are transported by pipeline from Texaco Ltd on Canvey Island and from the two oil refineries on the mainland. Helicopters from the site landing pad survey the pipelines.

The Plants of Concern British Gas Corporation Methane Terminal imports and stores about fifty shipments of 12,000 tonnes of liquefied natural gas (LNG) gas from Algeria each year, using two specially designed ships. The fully refrigerated liquid gas is pumped ashore from the ships to above-ground and in-ground storage tanks with 100,000 tonnes total capacity. Some LNG is road transported, but generally it leaves the terminal in vapor form by pipeline. Occasionally LNG-carrying ships are commissioned which involves cooling the cargo tanks with LNG from the terminal. The terminal is also used for the storage of liquefied butane brought by ships. About 200 people work at the terminal. Texaco Limited, Canvey Island tank farm on the west side of the methane terminal is used to import petroleum products by sea via the two jetties, store and distribute them by tanker-trucks and sea, but mostly by the U.K. oil pipeline. The storage capacity is 80,000 tonnes of petroleum products employing about 130 people. London and Coastal Oil Wharves Limited bulk stores, in tanks, a variety of petroleum products and other substances that are flammable or toxic. Some tankage is leased to Texaco Limited which is connected into the UK oil pipeline for transfer from the site. Products also are received by road and sea. The storage capacity is more than 300,000 tonnes with about fifty people employed.

429

Applications of PSA

Fig. J 1.4-1 Map of the Canvey Island/Thurrock Area

Mobil Oil Company Limited, Coryton occupies three adjoining sites on the mainland of Thurrock bordering the Thames and Holehaven Creek: the oil refinery, a bulk distribution depot associated with the refinery, and a large research and technical services laboratory. About 800 people are employed. Crude oil is imported by sea, stored in tanks for distillation into components which are either transferred directly to storage tanks, or chemically reacted into other products. From the storage tanks holding more than 1,500,000 tonnes, the products are distributed by pipelines, sea, road, and rail. Calor Gas Limited, Coryton occupies a small site employing about 100 people to fill cylinders with LPG which is supplied by pipelines from both of the nearby refineries and stored in its seven tanks 350 tonnes total capacity. Large numbers of portable cylinders of all sizes, full and empty, are on the site totalling about 500 tonnes of LPG. These are transported by road; gases are transported in tank trucks. Shell UK Oil, Shellhaven has the largest sites, about two miles along the Thames by about one mile across at its widest part and employs about 900 people. Crude oil, imported by sea, is transferred into storage tanks for distillation into components that are transferred into storage tanks, or chemically reacted into other products. The capacity of the storage tanks for hydrocarbons is more than 3,500,000 tonnes. The products are shipped by pipelines, sea, road, and rail. A large storage tank is used for storage of up to 14,000 tonnes of liquefied ammonia which is imported exclusively by sea and shipped from the area by sea, road, and occasionally rail.

430


Fisons Limited, Stanford-le-Nope is at the western extremity of the area and employs about 80 people in the production of strong solutions in water of ammonium nitrate from anhydrous ammonia. The liquefied ammonia is received from outside of the area in rail tankcars, stored, and partly refrigerated in a large spherical tank. The strong ammonium nitrate solution, produced on site, by reacting ammonia and nitric acid is stored in two large heated tanks. It is transported off-site in special tank trucks. Explosives are trans-shipped at Chapmans Anchorage in the River Thames off the eastern end of Canvey Island. There is also a specified anchorage for ships carrying explosives at the opposite end of the area. This more sheltered anchorage for emergencies, such as bad weather, is well outside the area of the investigation being at least one mile south of Mucking Creek. Ships in passage travel fairly close to the jetties and sea walls of the river bank within the area. All vessels within the estuary are navigated under requirements of the Thames Navigation Service of the Port of London Authority. 11.4.1.2 Methodology All members of the investigating team were appointed to be inspectors by the Health and Safety Executive. This enabled them to make the necessary inquiries. Ail facilities and their hazardous substances in the area were familiar to the HM Factory Inspectorate. The facility operators, local authorities at county and district level, the Port of London Authority, and many local organizations and members of the public provided information, some as a result of advertisements in the local newspapers informing readers of the scope of the investigation that invited submissions. The investigating team was reassured to find that the managements were responsive and knowledgeable of operational safety, codes of practices and design and construction of plant and facilities for hazardous materials processing, handling, or storage. However, none of the companies had systematically examined and documented those few potentially serious events which might cause accidents among people in the surrounding community. In the absence of this documentation the first major task of the investigating team was to identify and analyze from first principles the routes by which single or multiple accidents could affect the community. To carry out the assessment, the investigating team proceeded to: 1, 2, 3, 4, 5,

Identify any potentially hazardous materials, their location and the quantities stored and in process Obtain and review the relevant material properties such as flammability and toxicity Identify the possible ways in which failure of plants might present a hazard to the community Identify possible routes to selected failures typically involving: operator errors, equipment failure, plant aging, corrosion, over-filling, impurities, fire, explosion, missiles, and flooding Quantify the probability of selected failures and their consequences

For probabilities and consequences, the investigating team used data they had and information from many sources, including:

431

Applications of PSA

1, 2, 3. 4, 5. 6. ?. 8.

U.K. industries, including oil, chemical and other process industries, and transport Government agencies concerned with fire, and road, rail, sea and air transport Professional and industry organizations International safety conferences e.g. loss prevention in the process industries, ammonia plant safety, and hazardous materials spills Insurance organizations e.g., Lloyds, Det Norsk Veritas, and Fire Protection Association Foreign and international agencies, e.g., U.S. Coast Guard, U.S. Department of Transportation, OECD, and EEC Specialized research laboratories Experts Several special projects were initiated for this study:

1. 2. 3, 4. 5, 6, 7, 8, 9, 10. 11. 12.

History of identified storage tanks and their possibility of failure Probability of particular storage tanks or process vessels being hit by missiles caused by fires or explosions by fragmentation of rotating machines or pressure vessels, or transport accidents Effects of vapor cloud explosions on people, houses, engineering structures, etc. Evaporation of LNG from within a containment area on land or from a spill on water Special problems of frozen earth storage tanks for LNG and the effect of flooding Study of possible failures in handling operations Benefits and practicality of evacuation Sea-wall and its chance of being breached by subsidence, explosion or ship impact, timing consideration in flood Statistics of ship collisions and their severity, groundings, etc. Reliability analysis of fluid handling practices, ship to shore, and store to road vehicles and pipelines Toxicology of hazardous substances Lethal range for releases of toxic or explosive materials such as an ammonia spilt on water or land, or explosion or conflagration from a cloud of methane or liquefied petroleum gas

Other projects, mostly of more general application, were commissioned as the investigation developed. For example, the explosive behavior of clouds of liquefied petroleum or liquefied natural gas. Whether ammonia would rise as a light gas or slump from evaporative cooling. Potential hazards were identified early in the study stemming from the handling, processing, or storage of flammable liquids, ammonia, LPG, LNG, and hydrofluoric acid (HF). The degree of hazard, the extent of travel, and the number of people at risk, are all related to the large quantities of these materials on the various sites. Risk

Risk depends on toxicity, design, and the competence of management at each site. Thus, management is responsible for hardware, work practices, and the selection, training, duties, and

432


interrelationships of personnel. It must not only audit the plant but also the organization and its competence. In the absence of company documentation of the hazard potential of their plants and procedures and methods it was necessary for the investigating team to identify and analyze from first principles the routes by which a single or multiple accident could affect the community. The assessment of risk in a complex situation has uncertainties that are best expressed numerically. The team should quantify the probability and consequences of various types of accidents. This enables qualitative (large or small) expression of risk as well as numerical representation. To say that the probability is 1 in 10,000 of killing 100 people as compared with a probability of 1 in 100 of killing 1,000 people is much more meaningful than saying the chances of these types of accidents occurring are "very remote" or "quite high." The team made best estimates of particular events expressed as 1 in 10,000 per year. Quantitative assessment requires historical data which may be suspect for two reasons. There is the possibility that there are latent accidents not in the database. It is possible that past accidents have been rectified and will not recurr. In the absence of data, judgment based on experience and speculation must be used. Notwithstanding this weakness, the quantitative approach was adopted. The investigating team identified situations that could cause a number of public casualties. Events limited to the employees or which might cause single off-site casualties were not included in the assessment. Typical events that are considered are fire, explosion, ship collision, and the failure of pressurized storage vessels for which historical data established the failure frequencies. Assessment of consequences was based partly on conservative treatment of past experience. For example the assessment of the number of casualties from the release of a toxic material was based on past history conditioned by knowledge of the toxicology and the prevailing weather conditions. An alternative used fault trees to estimate probabilities and identify the consequences. Credit is taken in this process for preventative measures in design, operation, and maintenance procedures. Historical data provide reliability expected from plant components and humans. Both these methods have weaknesses. The historical data, implicit in both, may not be appropriate for the component in the assumed environment for the particular circumstances considered and may be irrelevant because of design rectification based on knowledge of previous failure. The broad approach may then be unduly pessimistic. On the other hand, the fault tree may fail to identify a primary cause which may have been missed by the plant designer to underestimate the probability of failure. The fault tree approach also takes credit for the preventative measures which may not be present in practice. The broad approach is likely to overestimate the risks because of insufficient account of preventative measures. The PSA team used the broad approach, recognizing that more accuracy may be attained by detailed industry studies.

Confidence Limits Confidence limits for the conclusions cannot be expressed simply because of the complexity of hazard assessments. The estimation of uncertainties is itself a process subject to professional judgment. However, the team's estimates of probability are believed to be realistic, but may be pessimistic by a factor of perhaps two or three, but less than a factor of ten. Uncertainties also exist 433

Applications of PSA

in the estimation of the consequences of any particular accident sequence e.g. in the health and debilitating effects of exposure to varying concentrations of toxic substances.

Risk Comparison Accident statistics show that individuals in an industrialized society are exposed to widely differing levels of risk according to age, sex, occupation, location, and recreation. There is not and cannot be equality in the levels of risks, from natural or man-made sources. For example, there are 18,000 accidental deaths per year in Great Britain (1976) of which 7,000 are traffic accidents or a probability of 1.3E-4 /yr if equally shared. The risk is not equally shared; it is 3 to 4 times lower for those who do not ride in cars; it is very much higher for young males between 18 and 25, Similarly, the risk of dying from an accident at home is 1.2E-4 /yr again the risk is not shared equally - 70% is carried by the very young and the elderly. The risk of a fatal accident at work is 0.3E-4 /yr. The chance of fatal injury is 11 times greater for workers in some occupations than it is for those in others. These figures relate to the risks to an individual. Societal risk is more concerned with a single accident causing many deaths than with many accidents causing the same number of deaths. Part of this concern stems from public belief in the rectifiabiiity of high consequence accidents. In practice, the overall risk to the individual is affected slightly by the risk from high consequence accidents. Most of the 18,000 accidental deaths in Great Britain arise from accidents in which only a few people die at a time. In some countries natural occurences kill thousands even hundred thousands, but little can be done to rectify nature and continue to live in these locations and the probability is not perceived to be high. 11.4.1.3 Major Hazards Attention focused on events that cold release a quantity of flammable, explosive or toxic vapors, hence, operations involving toxic liquefied gases such as ammonia and hydrogen fluoride, and flammables such as LNG and LPG. Ammonia Ammonia, when released is a toxic gas with little flammability. It is imported by sea into the 14,000 tonnes capacity tank at Shell UK Oil where the refrigeration maintains the temperature below the boiling point of the gas (33° C). Three ways were identified whereby several hundred tonnes of liquid ammonia could be released into the river to vaporize and disperse. The worst accident would have an accompanying explosion or fire on an ammonia carrier berthed at the unloading jetty. Next in order of severity is a ship collision and spillage into the river near the unloading jetty. The consequences of a collision between ships occurring within the area but not near the jetty were also calculated. The team suggested mitigations. For example, the consequences of an ammonia release could be markedly reduced by a reliable and quick-acting water spray system. The probability of damage due to ship collisions could be reduced by a factor of five by a speed limit of eight knots. Evacuation of the potentially affected is practicable and effective.

434


Liquefied ammonia is delivered in rail tankcars to Fisons Limited for storage in a 1,900 tonnes spherical tank at -6° C. Several hundred tonnes of liquefied ammonia could be released on land if either of the two storage tanks, at Shell UK Oil and at Fisons Limited failed. The consequences of failure of the Shell tank would be minimal, because a high concrete wall to contain the contents and limit the heat transfer and consequently the rate of evaporation of the liquid. Such protection has not been provided. Because of the storage under pressure there are numerous ways the tank could fail from material defect to missile. The spillage of 50 to 100 tonnes, could kill people if not promptly evacuation. Hydrogen Fluoride Hydrogen fluoride is at present stored in bulk and used at only the Shellhaven refinery, but future use is envisioned. Hydrogen fluoride boils point 19° C but stored and handled as a liquefied gas. Its vapor is highly irritating and toxic. A cold cloud will be denser than air in the early stages when released but will become neutral or buoyant as it warms with dispersion. This assessment assumes negative buoyancy Hydrogen fluoride is a component of the reaction to make the detergent alkylate plant at the Shellhaven refinery. The plant has 20 tonnes of hydrogen fluoride in several vessels operating above the boiling point of hydrogen fluoride. In addition, the plant has two 40 tonnes capacity store tanks to contain hydrogen fluoride to make up process losses that is delivered to the plant in tank trucks. It is assessed that the design and construction would withstand the overpressure resulting from an unconfined vapor cloud explosion. A water spray for the storage tanks and operating plant would mitigate a release. Liquefied Natural Gas LNG is predominantly methane, not toxic but flammable in air. Liquid below -161° C is delivered to the methane terminal in shiploads of 12,000 tonnes and is transferred into either four in-ground tanks, each of about 20,000 tonnes capacity or eight above-ground tanks, six with 4,000 tonnes capacity and two with 1,000 tonnes capacity. The LNG is refrigerated below the boiling point of the gas mixture. If LNG were released and cloud ignited the accident would be serious. If the cloud did not ignite on site but drifted to a populated area and then ignited, the number of casualties would be be much greater. Ignition sources are strictly controlled at the terminal so on-site ignition was not considered An explosion in the engine room of an LNG carrying ship berthed at the jetty could release vapor cloud, whose explosion would have serious consequences. No amelioration was suggested by the team. Release of cargo, from ship collision was discounted because of the eight knots speed limit. Spillage of LNG within the containment walls of the aboveground tanks was considered as was roofs collapse of the in-ground storage tanks if the river were to overtop the sea wall causing a substantial release of vapor as the tanks flooded. This effect could be eliminated by higher containment walls. Risks from the commissioning of new LNG-carrying ships and from frozen ground LNG storage tanks were examined without identifying major problems.

435

Applications of PSA

Liquefied Petroleum Gas

LPG is a mixture of flammable hydrocarbons which are gas at normal temperature but liquid under pressure or when cooled below the boiling point at atmospheric pressure. Two mixtures are in common use, commercial propane and commercial butane. Large quantities are stored and handled at: British Gas Corporation methane terminal, Shell UK Oil, Mobil Oil Co. Ltd, and Calor Gas Ltd. The last also fills and handles large numbers of portable LPG cylinders. There are three aboveground tanks at the British Gas Corporation methane terminal for storage of liquid butane by refrigeration below the boiling point of 0° C. Two tanks have a capacity of 5,000 tonnes each, third's capacity is 10,000 tonnes. A pipeline from the tanks crosses the area. A substantial quantity of LPG could be released from any one of the three refrigerated storage tanks to form a large flammable cloud that could ignite and explode, causing casualties in the vicinity of the terminal. The pipeline from these tanks could fail and cause casualties. At the Shell UK Oil refinery the storage capacity for LPG is 5,000 tonnes. The gases are stored at ambient temperature. Most of the storage capacity of four spherical tanks for butane is 3,200 tonnes. The total capacity of the four spherical tanks for propane is 1,600 tonnes with each tank holding about 400 tonnes. In addition, three horizontal cylindrical tanks store about 400 tonnes of mixed liquefied petroleum gases, each tank holding about 135 tonnes. At the Mobil Oil Co. Ltd. refinery, the storage capacity for liquefied petroleum gases is about 4,000 tonnes, stored under pressure at ambient temperature, and it is proposed to double this in the near future. Later it is intended to add to these tanks, a single tank in which about 5,000 tonnes of the liquefied gas would be stored, fully refrigerated, at a temperature lower than the boiling point. Fifteen tanks are in use at present, of which ten are relatively small horizontal cylindrical tanks and the others are spherical tanks ranging in capacity from about 250 tonnes to one of about 1,000 tonnes. Calor Gas Ltd. stores a small quantity of liquefied gas because it can be delivered readily by pipelines from the neighboring oil refineries. The five tanks each storage about 60 tonnes capacity at ambient temperature. Three are used for propane and two for butane. The total quantity of gas contained in filled cylinders averages 500 tonnes. The possibility that the storage tanks could fracture has been calculated. At the Shell UK Oil refinery, the storage vessels are located in two groups, one close to the vehicle filling position. Consideration is given to an explosion in the filling area sending a shock wave to the other storage area, failing the tanks to generate a large vapour cloud to drift off-site to a populated area before ignition with serious effects. The possibility missile impact failing a storage tank at the Shell site was assessed. Similarly missile impact failure was assessed at the Calor Gas Limited site. An assessment was made of a major fire at this LPG cylinder filling plant violently projecting some of the filled cylinders from the site to impact on the Mobil plant, however it seems that the missiles lack sufficient energy to penetrate the storage units but pipes may be fractured. Large clouds of vapor could be generated if LPG were released from an explosion on a ship transferring LPG at one of the Shell or Mobil jetties or the Occidental jetty, or from a collision between an LPG-carrying ship near the unloading jetty and another ship. The consequences of these events would be serious, and little action could be taken to lessen the probability of the explosion, although observance of the eight knots speed limit should reduce the probability of ship collisions. 436


Table 11.4-1 Frequency /1 0,000 Years of Exceeding Maximum Casualties for Existing Facilities

10

Max. Casualties Status*

a

1500

b

a

4500

3000

b

a

b

6000

18000

12000

a

b

a

b

a

b

a

b

3.8

0.5

1.2

0.3

0.8

0.2 0.1

Shell UK Oil

7,8

3.3

5

1.9

3.6

1.3

2.7

0.9

Mobil Oil Co. Ltd.

1.4

0.3

1.1

0.2

0.7

0.1

0.3

0.1

British Gas Corp.

14.7

4

5.4

1.5

3

1

1.6

0.7

0.4

0.4

0.2

0.2

0.1

Fisons Ltd.

3.6

1

2.4

0.5

l.i

0.3

0.8

0.1

0.3

O.I

o.t

Texaco Ltd. and London & Coastal Oil Wharves

3.9

2

3

1

1.7

0.6

1

Total

31.4

0.6

3.1

8.6

17

2

0.4

1.5

4.2

10.8

2.9

6.1

0.3

Frequency /1 0,000 of Exceeding Maximum Casualties for Proposed Facilities Mobil Oil Extension

2.8

0.4

Occidental Refinery

2.9

United Refinery

1.4

Texaco Ltd. and London & Coastal Oil Wharves

9

Total

16.1

1.7

0.2

0.9

2.2

0.9

0.9

1.1

0.1

0.7

1.7

0.6

0.5

7.3

2.2

12.1

0.7

0.1

0.3

0.5

1.4

0.4

1.1

0.3

0.8

0.2

0.7

02

0.3

0.2

0.1

1.4

0.3

1

0.2

0.8

0.2

3.6

1.5

6.9

0.2

0.1

0.9

0.9

3.2

0.6

* Columns labeled "a" are the assessed exceedance probabilities before safety improvements; Columns labeled "b" are the assessed exceedance probabilities after safety improvements

Flammable Liquids

Large quantities of flammable liquids are storaged on Canvey Island at Texaco Ltd and at London and Coastal Oil Wharves Ltd., and at the two operating refineries on the mainland of Shell UK Oil and Mobil Oil Co. Ltd. Proposed oil refineries for Canvey Island would also store large quantities of flammable liquids. It is conceivable that an explosion could damage the storage tanks, releasing the flammable substances which might ignite. If many tanks failed, their contents could overflow the dikes and burning liquid could flow in drainage channels to ignite houses. Such accidents include the explosion of vapor released in the atmosphere from an explosion of an LNG-carrying ship berthed at the methane terminal or of an LPG carrier berthed at the Occidental jetty. Other possible causes include a process plant explosion at the proposed Occidental refinery, or spontaneous failure of LPG storage tanks at proposed refineries. Other possibilities are an explosion of a barge or ship carrying explosives stranded on the opposite shore. These probabilities were assessed. The severest consequence of such a fire could be prevented on Canvey Island by constructing a simple secondary containment wall around the Texaco Limited and London and Coastal Oil Wharves Limited installations and around proposed oil refineries.

437

Applications of PSA

Ammonium Nitrate

Ammonium nitrate is made at Fisons Ltd and stored in solution in two heated tanks to prevent crystalization. One tank holds 3,100 tonnes and the other 6,200 tonnes of 92% aqueous ammonium nitrate solution. Trains laden with oil refinery products from the Mobil and Shell refineries pass the factory on a near embankment. A derailment could spill and ignite hydrocarbons from a rail tank car to explode an ammonium nitrate storage tank. Suggestions were made to mitigate or prevent such a domino effect 11.4,1.4 Societal Risk Many of the accidents considered in the investigation could occur without causing any significant public casualties. However, if the conditions at the time of the accident were sufficiently unfavorable, the number of deaths among the public could range from tens up to thousands (Table 11,4-1). Table 11.4-1 is the summarized population risk assessed by the study team. It is in frequency per 10,000 years of an accident at the indicated facility that causes casualties exceeding the indicated limit. Reference should be made to Canvey (1978) for details. 11.4.2 PSA of a Butane Storage Facility (Oiiveira, 1994)

Introduction

A deactivated butane pressurized storage facility with two 750 m3 and two 1,600 m3 spheres was considered for partial activation of the two smaller spheres. A safety review showed that aspects of the facility did not comply with with current standards of PETROBRAS regarding layout and separation. A PSA was performed with the following objectives: • » • •

Assess the public and workers risks imposed by operation of the facility as it is; Compare the results to existing international acceptability criteria; Propose and evaluate risk reduction measures; and Evaluate whether it is acceptability with risk reduction measures, or move the facility to a recently refurbished LPG storage facility.

PSA

Risks were expressed as triplets: <what can go wrong I frequency I consequencesx The first element of the triplet was found using accident records and a PHA. The databases used were MHIDAS (1992) (>5000 accidents) and ACCIDATA (>1,500 mostly Brazil). The PHA was performed by personnel from REDUC (facility operator) and PRINCIPIA (the PSA vendor). About 170 basic initiating events (ruptures of pipes, flanges, valves, spheres, pumps and human actions) were grouped into 12 initiators by equivalent diameter, pressure, flow type and rupture location. The second triad element was determined from international frequencies for the basic initiating events. One fault tree for sphere rupture was constructed and evaluated using the fault tree program FTW(1991).

438


The third triad member was evaluated from the accident scenarios involving failure or success of existing protection systems, daytime and nighttime conditions, wind speed and direction, and ignition sources. There were 1,474 different accident scenarios were evaluated, involving BLEVE's, flash and pool fires and unconfined vapor cloud explosions (TNO, 1980 and Colambrander, 1933). The consequences of each scenario were calculated for the public and workers. A risk assessment program VULNER-f was developed by PRINCIPIA to perform scenario frequency and consequence calculations. The accident scenarios were generated by the program from information provided by the analyst, A square grid overlaid the site. Each square was associated with the population contained therein and the ignition sources. Cells were subdivided for greater resolution as needed. The fatality conditional probability at each cell center is associated with the scenario frequency to produce the value of the individual risk at that cell. The program interpolates to draw the contours of individual risk around the facility. F-N curves and average societal risks are found by coupling results to the population in the cell. The ranked scenarios help in proposing risk-reduction measures. Risk Results As the Facility Is Contours of individual risks at frequencies of: lE-4/y, lE-5/y, and lE-6/y were obtained, at approximated radii of 200, 500 and 700 m around the facility. The F-N curve for the public showed >10 in 2E-4/y, and > 100 in 7E-5/y, with a maximum of 275 fatalities. The existing facility public risk is2.1E-2fatalities/y. Risk Reduction Table 11.4-2 shows risk reduction measures and their impact on public risk, their cost, and the cost per death averted. From this table, with the exception of the last one (because of high cost), the measures are practical for implementation. Table 11.4-2 Risk Reductions and Costs

Conclusions

Measure

It was concluded that: 1. The operation of existing facility imposes an unacceptable social risk to the public based on criteria used in the Netherlands and Denmark. 2. After the implementation of all risk-reduction measures, the public risk is nt>t acceptable (Denmark criteria), mainly due to low frequencies/high consequences (highly populated area). After these

Test liquid blockage valves every 3 months Water injection directly into the manifold eliminating a valve and reducing the valve size for drainage Elevate and slope ground under spheres Valves removal at the pump discharge Explosion-proof control room and operator always.present in control room Only one product receiving line; removal of other Nafta pipeway relocation Removal of neighboring liquid fuel tanks All risk reduction measures

439

Risk Cost $/death reduction $us averted fatal./y 5.1E-5 0 3.3E-3 2.8E4 1.1E6

1.3E-2 1.3E-4 1.1E-3

4.6E5 5.0E6 1.0E4 LIE? 1.0E5 1.3E7

1.1E-4

1.1E4 ! .4E7

6.3E-3 4.1E5 2.4E-2

9.5E5 2.0E7 3.1E6 1E10 4.6E-6 2.6E7

Applications of PSA

measures, the public area subjected to levels higher than l.OE-5 (the maximum value for acceptability in England) is relatively small being mainly employees of adjacent companies, 3. Because the risks were not reduced by the risk-reduction measures to an acceptable level, relocation of the butane storage to the refurbished LPG facility is attractive.

11.4.3 Comparative Applications of HAZOP, Facility Risk Review, and

Table 11.4-3 HF Alkylation HAZOP Results Hardware 1, Designate/install emergency isolation valves in the alkylation unit and install remote switches in the alkylation unit control room so that operators can close these valves during emergencies 2. Install remote switches in the alkylation unit control room to shut down the major pumps in the alkylation unit during an emergency 3. Designate critical process alarms in the alkylation unit and ensure that these alarms are installed independent of equipment control loops

Fault Trees

4. Review the design bases for unit relief valves and the flare system to ensure that they are still valid

Montague (1990) addresses the problem of selecting the appropriate analysis method for chemical process safety. He describes three methods and provides an example of each. Chapter 3 describes the methods (except facility risk review), hence, we go to examples of each.

5. Evaluate ways to prevent backflow in critical lines between process equipment

11.4.3.1 HAZOP of an HF Alkylation Unit

6. Evaluate making the alkylation unit control building a "safe haven" during hazardous material releases administrative action items Administrative Action Review the acid unloading system and its procedures to ensure that adequate safety precautions are included for minimizing potentially hazardous incidents during acid unloading operations

System Description 2. Establish/enhance consistent programs to A large oil refinery had a failure in their periodically inspect and test the engineered defenses that are designed to protect against hazardous upsets alkylation unit resulting in a significant release in the alkylation unit of hydrofluoric acid (HF). This incident and 3. Investigate ways to improve the control of others in refineries during recent years prompted replacement materials installed in the alkylation unit members of the hydrocarbon processors to turn during turnarounds and routine maintenance to HAZOP to better understand their risks. 4. Investigate ways to reduce the potential for Figure 11.4-2 shows process flows for an external impacts to damage process piping while the HF alkylation unit. The three sections are: 1) alkylation unit is operating reaction, 2) settling and 3) fractionation. In the 5. Evaluate the acid relief neutralization system in HF reaction section isobutane feed is mixed with the alkylation units to ensure its adequacy for neutralizing olefin feed (usually propylene and butylene) in design basis relief valve discharges and unit ventings approximately a 10 or 15 to 1 ratio. In the 6. Enhance refinery emergency procedures by specifically addressing accidental releases of acid presence of the HF acid catalyst the olefms react to form alkylate for gasoline blending. The exothermic reaction requires water cooling. The hydrocarbon/HF mixture goes to the settling section where the denser HF is separated by gravity and recycled back to the reaction section with fresh acid to compensate for losses. The hydrocarbon is fractionated in several towers where it is 440


separated into a recycle Coolant Out Recycle Isobutane isobutane stream and I. .. . £~} _.~ ~ ~~1 Propane three products: alkylate, Olefin Feed i ; Settling Fractionation i Normal Butane propane and n-butane. Isobutane Feed ( Section I ^ Section Section i_AI_ky_ate_ This section also . -+purifies the products by } L Recycle Acid removing the small i_ |Sobutane Feed Coo|ant |n Fresh Acjd s Jnt Add amounts of HF in the Fig a.4-2 Alkylation Process product stream and returning the acid to the reaction section. HAZOP The HAZOP team consisted of a HAZOP leader, scribe, process engineer, senior operator, and a safety engineer. Previously, the HAZOP leader collected information on the process design (e.g., P&IDs, operating procedures, emergency procedures and incident reports) for distribution to each team member. The leader sectioned the process and identified process deviations prior to the HAZOP. The actual HAZOP required a 1-week meeting and a 3-day meeting. During the first meeting, the team "HAZOPed" each section of the process, identified process upsets with significant consequences, and made recommendations for safety improvements. In the second meeting, a month later, the HAZOP team resolved open issues from the first meeting and examined sections of the process not reviewed in the first meeting. The HAZOP took 3 calendar months to complete. However, preliminary recommendations for system safety improvements were available after the second HAZOP meeting. The HAZOP required about 2 staff-months of effort. In addition, the HAZOP leader and scribe spent another 3 staff-months in preparation and documentation. Results Sixty recommendations were made for improving the safety of the HF alkylation unit. The suggestions ranged from minor piping changes to installing remote control isolation valves to changing emergency procedures. The recommendations can be divided into: hardware and administrative. Hardware requires new or modifies existing hardware; administrative changes require modifying procedures, initiating or enhancing programs - usually at less cost than hardware. Table 11.4-3 lists 12 of the 60 suggestions for HF alkylation. 11.4.3.2 Facility Risk Review (FRR) of a Mining Operation FRR Procedures A facility risk review (FRR) is intermediate between a qualitative HAZOP and a quantitative risk assessment (QRA) achieved by broad probability and consequence classifications. Although not a risk assessment, an FRR uses PSA to get optimum risk cost-benefit.

441

Applications of PSA

QRA is generally resource intensive. FRR, is much less although it uses the framework of QRA for screening and ranking systems by relative risk using order-of-magnitude estimates of the frequencies and consequences of events. It incorporates plant experience and industry data to estimate the potential for future losses. Art FRR consists of the following: • « * « »

Failure modes and effects analysis Consequence assessment Frequency assessment Risk categorization Recommendations

Background Description

and

System

Table 1L4-4 Recommendations from FRR of Mining Operation Mining - Develop and emphasize maintenance work plans on large mining equipment - Emphasize and improve fire protection for mine equipment areas, - Ensure that the fire protection systems in the major equipment electrical rooms are adequate and are periodically tested - Stop bringing the explosives truck through process and administrative areas Ore processing - Evaluate the current operability of critical items for the conditioning drums - Consider providing remote shutdown capability for the charge pumps - Evaluate capability to respond to major process leaks in the first or second stage pump areas - Consider a foam fire protection system for the first stage pump area - Consider moving the chemical storage tank to an outdoor location - Develop a contingency plan for responding to collapse or blockage of the Area 2 sewer line from the building to the decant pond Refinery area - Consider installing remotely operated isolation valves in the bottoms piping connected to vessels containing large inventories of hot solvents - Consider a test program for periodically checking critical instruments and trip devices - Consider a test procedure requiring periodic cycling of MOVs - Consider a policy of independent inspection and verification of work performed by maintenance - Review the instrumentation/trip designs for all furnaces in the refinery area - Evaluate whether the interlocks on the swing valves are adequate to prevent operators from inadvertently mispositioning them - Review the compressor building ventilation system to ensure that it has adequate capacity to maintain acceptable temperatures in the compressor bays - Consider a test procedure to periodically check the operation of an important steam flow control valve and the position of its associated bypass valve

Three years ago, a fire in a large mining operation resulted in Utilities area tens of millions of dollars in - Evaluate alternatives for protecting the facilities from events that can result equipment damage and a in plant freezeup - Evaluate alternatives to upgrade the raw water system valve box and piping half-billion dollar loss from - Evaluate the integrity of the old cooling water loop piping, and identify ways months of lost production. to protect against its failure Previously, the facility had several - Improve the current capability to isolate steam lines leaving the powerhouse to ensure that the steam system can be protected from piping ruptures outside multimillion dollar accidents, and the powerhouse near misses. After each accident, - Provide an emergency response plan for flammable gas leaks in the investigations were made and powerhouse, including methods for rapidly isolating potential ieaks or ruptures corrective actions taken. However the large fire precipitated a risk evaluation of the entire mining complex to find latent accidents. The mining facility consists of four major operations: 1) mining, ore extraction and transportation, 2) ore processing - treatment with chemical solvents to remove minerals, 3) removing impurities and 4) utilities e.g., electricity, steam, water, air and natural gas provided by the facility's power plant and by off-site suppliers. Accidents in any of these operations can stop the whole process.


The FRR Analysis Each of four teams for each mining operation consisting of a risk analyst and engineers and operators performed the FRR. The risk analyst provided the FRR expertise and directed the analysis of the operation; facility engineers and operators provided operational knowledge and estimated the likelihood of equipment failures and their impact on facility operations. Following the FRR procedure, each team performed an FMEA, to identify costly accidents. Each accident was assigned a frequency category and the cost of equipment damage, outage time and percentage reduction in facility output was estimated. The frequency and cost were combined to estimate the accident risk. From the risk and the insights gained while performing the analysis, the FRR teams identified recommendations for reducing the likelihood of multimillion dollar accidents. The FRR required 8 calendar months to complete. It was performed by a team of three risk analysts who expended 2 staff-years of effort conducting the analysis. During the FRR, the mining facility provided 15 people who collectively expended about 4 staff-months of effort providing the risk analysts with facility design information and estimating accident impacts. Results The FRR teams identified more than 1,600 potential accidents of which 1,000 were considered significant enough to be assigned a frequency and consequence category. These accidents were then arrayed by frequency and dollar cost to show 165 accidents of greatest concern. The FRR teams recommended actions to reduce the likelihood of these 165 accidents. The risks expressed as M$/y for the four operations are mining: 3.2, ore processing: 2.9, refinery: 46.1, and utilities: 8.5, to give a total risk of 60.8 M$/y. Some recommendations are given in Table 11.4-4. 11.4.3.3 Quantitative Risk Assessment of a Chemical Reactor Background and System Description A chemical company was considering a larger reactor to expand production. Because of industry reported accidents with this process, a HAZOP was performed that identified the potential for a violent reaction with deadly consequences. A QRA was conducted to better understand the risk of expansion and to determine additional safety needs. The reactor system (Figure 11.4-3) consists of a 5,000-gallon vessel, an agitator and pumps for circulating cooling water through the reactor jacket. Chemicals X and Y are fed at a controlled rate to the reactor, where they react exothermically in the presence of a catalyst to form the product. If the temperature gets too high, the reaction may runaway. Causes of high temperature (identified in the HAZOP) included loss of cooling, loss of agitation, and a high ratio of catalyst to chemical feed. Proposed safeguards include 1) an emergency shutdown system that automatically shuts off the feeds to the reactor, increases cooling, and dumps a reaction quenching poison into the vessel if required and 2) a manually controlled dump line to a quench tank.

443

Applications of PSA

QRA

The QRA was Air conducted by risk FE2 FIC2 analysts and design FeedX —U personnel to determine the probability of explosive releases of FeedY FE4 the chemical. Fault tree CtAa**sl analysis identified several combinations of equipment failures and operator errors that could cause the top event (reactor explosion). Failure data were obtained from plant experience and industry databases to quantify the fault trees to estimate the frequency of reactor explosions. The fault trees suggested 11.4-3 Proposed New Chemical Reactor several safety irnprovernents. These suggestions were tested by incorporating them into the fault tree models to assess their risk reduction. Sensitivity studies were performed to assess the robustness of the analysis. Parallel to the frequency 1E-2 assessment, the consequences of the scenarios were calculated for the 1E-3 seffects on the public and plant personnel of chemical release through 1E-4 the rupture disc and fire and explosion. £ Gas dispersion models provided the J IE-S toxic effects of chemical releases, fire, | or unconfined vapor cloud explosion, o ie-e The affected areas were plotted on demographic maps to determine the 1E-7 s number of people affected. The QRA required 5 calendar 1E-8 0.001 100 0.01 0.01 months by two risk analysts. A total of Impact Factor 6 staff-months were required for Fig. 11.4-4 Case Studies of QRA Results completion. During the QRA, the

444


chemical company provided an additional 1 staff-month in gathering information and reviewing results, Results Suggestions for mitigation were tested using the consequence models to determine their efficacy, Sensitivity studies were performed to test assumptions on the frequency/ consequence curves. Case 1 in Figure 11,4-4, the base proposed reactor design, shows that an explosion affecting off-site personnel (consequences greater than impact factor 10) has a frequency of Table 11.4-5 Frequency (1/y) vs Assumptions about once every 10,000 years. Alternate Assumption High Low reactor designs, Cases 2-6, could lower Reactor volume (1E3 - 1E4 gal. 4.3E-S 8.5E-3 this by about 1000. Reactor pressure (5-50 psig) 1.1E-4 1.5E-4 These results showed manageExtra cooling capacity (10 100%) 8.1E-3 1 .3E-2 ment that the proposed larger reactor 2.9E-4 Emergency System Effectiveness (100 -70%) 8.5E-3 design had an unacceptably high risk. Reactor mixture dilution (50%/50%) 2.7E-7 8.5E-3 Design modifications can substantially reduce risk, none eliminate the possibility of adversely affecting the public. Only by reducing the reactor volume or by reacting the chemicals with a solvent (economic penalty) could consequences be reduced to on-site only. Table 11.4-5 shows some results of the sensitivity studies. Summary of QRA of the Chemical Reactor 1. The variation in risk between the designs analyzed is influenced more by differences in the consequences of the accidents than by differences in the accident frequencies. 2. The risk of a violent reaction causing a chemical release increases as the design volume of the reactor increases. 3. Improving the capability to detect a runaway reaction and terminate it (by emergency protection) significantly reduces risk. 4. The risk of a violent reaction decreases if the chemicals are mixed with an inert solvent that provides a heat sink and reduces the chemical inventory. 5. High-pressure can increase risk because of greater overpressure from a violent reaction, 11.4,3.4 Comparison of HAZOP, FRR and QRA

Montegue (1990) compares the three methods as presented in Table 11.4-6. 11.4.4 Probabilistic Safety Analysis of an Ammonia Storage Plant Introduction and Facility Description The following PSA of a refrigerated ammonia storage facility is from Papazoglou (1990a, I990b), An objective of the work was to test PSA as it had been applied to nuclear power

445

Applications of PSA

Table 11.4-6 Comparison of Some PSA Methods Hazards and Operability (HAZOP)

Facility Risk Review

Quantitative Risk Analysis

Focuses on one area or operation, and many types of hazards

Broad review of many areas or operations, many types of hazards

Involves many company personnel for short periods of time (ties up several people at one time)

Involves a few company personnel Involves a few company personnel for short periods of time (ties up one for short periods of time (ties up one or two people at a time) or two people at a time)

Provides a qualitative measure of risk Provides a coarse quantitative measure of risk

Focuses on a specific type of hazard

Provides an absolute quantitative measure of risk

Good screening of hazards/risks

Inefficient screening of hazards/risks Inefficient screening of hazards/risk

Subjective evaluation of recommendation effectiveness

Subjective evaluation of recommendation effectiveness

Cost/benefit analysis of recommendations

plants for applicability to chemical process facilities. Related papers are Papazoglou (1992, 1996). The facility stores ammonia to supply nearby fertilizer manufacturers. It is transported to the plant by ship, transferred and stored in the tank for transfer as needed. The facility mainly consists of a storage tank, a refrigeration system, a control system, and a pipe connecting the tank with the plants. Ammonia is transported and stored as a refrigerated liquid (-33° C) at atmospheric pressure. The storage facility operates in three phases: 1,

2, 3,

Transfer of liquid ammonia from the ship using a special pipeline to the thermally insulated storage tank. The transfer, requiring 20 hours, uses the ship's pumps; there are five transfers each year. The ammonia is in refrigerated storage up to 1,646 hours Ammonia is unloaded from the storage tank to either of the two fertilizer plants using three discharge pumps for 86 hours.

During each of the three phases a refrigeration system, consisting of three (3) compressors, two (2) condensers and one (1) separation drum, ensures that the ammonia is at its storage temperature. PSA

The methodology and the procedures consist of the following seven major steps: Hazard Identification, the main sources of ammonia that could release are identified and the initiating events (IE) that can cause accidents leading to the release of ammonia are determined. Three methods used for BE identification were: Master Logic Diagram, checklists, and HAZOP Accident Sequence Modeling using a logic model for the facility was developed. The model included all initiators of potential accidents and the response of the installation to these initiators. Specific accident sequences are defined in event trees consisting of an initiating


3.

4.

5.

6.

7.

event group, specific system failures or successes and their timing, and human responses. Accident sequences result in plant damage states that may or may not release ammonia. System failures are modeled in fault trees of component failures and human errors. Nineteen event trees were developed and thirteen were quantified. Data Acquisition and Parameter Estimation determines frequencies of the initiating events, component unavailability and probabilities of human actions were estimated from plant history. If insufficient, generic values were used including generic data from the nuclear industry (IAEA, 1988). In addition meteorological data and data on the population distribution around the plant were gathered and processed. Accident Sequence Quantification estimates the IE frequency. Specifically, the plant model built in the Step 2 is quantified by data from Step 3 according to Boolean algebra. Quantification may be a point-value calculation in which all parameters are deterministic, or as uncertain values known by their distribution function. Ammonia Release Categories Assessment consists of grouping accident sequences of the same failure mode into a plant-damage state. A plant-damage state is characterized by the quantity and type of release corresponding to the plant physical conditions at the time of release. Consequence Assessment calculates the atmospheric dispersion of the released ammonia, the assessment of the individual dose at each point around the site, and the construction of a dose/response model. Each ammonia release category might lead to different concentrations, hence, different doses and probabilities of consequences. An uncertainty analysis is performed for the distributed parameters for various model assumptions. Integration of Results - consists of integration of the model with results from Steps 4, 5 and 6, to determine consequences, probabilities and range of uncertainties. Two types of results were calculated in this study: individual risk as a function of distance from the installation, and isorisk curves. Both are risk indices and are related to the probability of death from ammonia inhalation,

Individual Risk The risk to an individual from operation of the facility was quantified as: isorisk contours (Figure 11.4-2 - loci of equal individual fatality frequency points) and maximum individual risk vs distance curves for the most exposed individual vs distance from the site (Figure 11.4-3). Uncertainty analyses were performed (not shown). The five types of accidents significantly contributing to the risk are failure and their mean frequency are: 1. 2. 3. 4. 5.

Piping between the ship and the tank during loading phase (3.8E-3/y), Ammonia storage tank from ammonia overpressure (1.1 E-3/y), Ammonia storage tank from an earthquake (1.3E-3/y), Piping between the storage tank and the fertilizer plants (5.9E-4/y), and Storage tank from underpressure (l.OE-5/y).

447

Applications of PSA

The largest contributor to individual risk is the failure of the piping between the ship and the storage tank during the loading operation because of the amount, the mechanism and the dispersion of the ammonia released. Next is storage tank failure from overpressure, and from an earthquake. Smaller contributions are from failure of piping between the storage tank and the fertilizer plants, and the tank failure from underpressure. The total mean frequency of a substantial ammonia release from the storage installation is 6.8E-3/y. Thus, on the average there will be one substantial release of ammonia every 150 years of operation. There is a 70% probability (one sigma) that the frequency of ammonia release will be less than its mean. Ammonia Release Categories A release category is a grouping of specific types of releases with similar characteristics. Here, two general types of ammonia release were defined: Category 1. Release of gaseous ammonia primarily from failure of Tank DK-101 by three plant-damage states: overpressure, underpressure and seismic load. For all three it was assumed that: » •

The tank fails at the welding seam between the curved roof and the cylindrical plate wall with break area, A. All gaseous ammonia in the tank at rupture escapes. This amount depends on the liquid depth, H.

The duration of the release depends on the break area among other things. For a given quantity of ammonia, there is a critical area A,,, below which gaseous ammonia is dispersed as a buoyant plume, above which it is dispersed as a heavier-than-air plume. The liquid ammonia depth in the tank, the size of the break, and the duration of release are treated as random variables. Tank failure from overpressure and seismic load are characterized by triplets of heights, H, equivalent areas, A, and duration of release corresponding to a particular release category. Tank failure from underpressure was associated with minimum ammonia in the tank, the break size and duration of release. In all cases, evaporation of the remaining liquid ammonia in the tank was considered. Category 2. Release of liquid ammonia from pipe failure for two plant-damage states involved the assumptions: • •

Ammonia is released at a constant rate (loading or unloading) for time T. The released ammonia forms a pool of refrigerated liquid which evaporates by heat transfer from the soil. A constant mass value was assumed for the evaporation rate and a heavier-than-air gas dispersion model was used.

The duration of the release was treated as a random variable for the uncertainty calculations. Consequence Calculations The atmospheric dispersion model for dense ammonia vapor evolves a slice of the plume, from the source to receptor (Kaizer, 1989;

448

P0=(j.5*[l+erJ\P-5)/lAl42] P = -35.9+1.85 *ln(c2 *?)

(11.4.4) (11.4-2)


Technica, 1988; Wheatley, 1988;Ziomas, 1989). Plume dispersion consists of two phases: the gravityslumping and passive dispersion period. Continuous releases with any time-profile and puff releases as of short duration continuous releases are treated using the release category and the weather conditions. Weather is also treated as a random variable. The probability of death of an individual (P0) exposed to an ammonia cloud is calculated according to equation 11.4-1, where erf is the error function and P (equation 11.4-2) is the probit value of ammonia, c is the concentration of ammonia in ppm, t is the exposure time assumed to be one-half hour. These calculations are integrated in the computer code DECARA (Papazoglou, 1990b).

11.5 Problems 1.

2.

3.

If a nuclear power plant loses its connection to the offsite load, it must shutdown because it cannot be cutback sufficiently that its electrical output matches its "hotel" load. Outline a PSA study to determine the risk reduction that might be achieved by switching in a dummy load to avoid shutdown and keep the plant online. If the containment holds, nuclear power plants present no risk to the public. Overpressurization of the containment is the failure mode that could allow direct release of radioactivity to the public. Design a risk reduction investigation of the benefits of releasing the gas pressure through an off gas processing system that removes the particulates. Many nuclear plants are connected to rivers such as Indian Point. Discuss accident sequences that could result in a PWR releasing significant radioactivity into a river. a) Outline the PSA steps that would be necessary to determine the probabilities and consequences. b) How could such an accident be mitigated?

449


Chapter 12 Appendix: Software on the Distribution Disk

The distribution disk located at the Butterworth-Heinemann website http://www.bh.com/ contains the following software for use on an IBM or IBM-clone personal computer operating in DOS, Windows 3.1 or Windows 95. The programs are small, operate in the DOS mode with minimal system requirements. It is recommended that a directory (folder) be constructed on your hard drive and copy them to this directory. No guarantees are made; use them if you find them useful. They are: 1. 2. 3. 4. 5. 6.

ANSPIPE Calculates pipe break probability using the Thomas Model BETA Calculates and draws event trees using word processor and other input BNLDATA Failure rate data FTAPSUIT Set of codes for finding fault tree cutsets, evaluating fault trees, calculating importances and performing uncertainty analysis LAMBDA Code for estimating failure rate for confidence intervals using a Chi-Squaredand an F-Number estimator. Also includes Gamma and Normal calculators. UNITSCNV Program for units conversion and relativity calculations

12.1 ANSPJPE Is an IBM-PC code to estimate pipe break and leak probabilities by implementing Thomas's procedures (Thomas, 1981). ANSPIPE aids the engineer guiding the inputting of information needed MAIN ANSPIPE MENU for a parametric study, predicting the leak and break probabilities, 1 Set Default File indicating the probabilities accor2 Read in Previous Pipe Segment Definitions ding to the specified pipe sizes of 3 Define the Pipe Segments large, medium, small and small4 Compute and Display the Pipe Failure Probabilities small and according to whether they 5 Plot the Results are submerged in pool water or not. 6 Print Results including Setup Data It presents this information on the 7 Record Pipe Segment Definitions on a Disk CRT screen, prints it or graphs it as 8 Quit a histogram. Figure 12.1-1 shows Select the Number of the Task to be Performed the main menu. The first selection Fig. 12.1-1 Main Screen for ANSPIPE

451

Appendix

creates and a default file for the large, medium and small pipe diameters, the type of steel, pipe wall thickness, number of circumferential welds per segment, replications, whether or not there are longitudinal welds, and the internal pipe pressure. If the default file previously was defined, selection 1 is skipped and the file is read in using selection 2. Selection 3 defines a segment with a title, the number of segment replications, type of material, internal pressure, diameter, the ASME critical wall thickness, and the segment length. Selection 4 computes the pipe failure probabilities, selection 5 plots the results, selection 6 prints the results, and 7 saves the definitions to a disk. The program has edit capability if changes are needed in an approximately correct setup, or a data file may be prepared and edited with an ASCII text editor. Both output and input files may be labeled for storage and retrieval or optionally the default name may be accepted.

12.2 BETA Event trees exhaustively explore the combinations of system failures that may follow from accident initiator through dendritic diagrams connecting initiator with plant damage state and by calculating the frequency of each accident sequence. They are the central element of PRA, but require supplementary text to relate the sequences to plant systems, and explain the logic and state assumptions. These tasks are accomplished by the integration of a popular word processor and the event tree analysis code BETA (Fullwood and Shier, 1990). Using the word processor, you write text that describes each sequence to the necessary depth and prepare an Event Table which indicates, by symbols, the operability of each system in the accident sequence and the judged fuel damage state. The matrix of symbols so formed is copied to another file, edited to remove spaces, BETA Main Menu additional information is added and the file is saved in ASCII format to provide input to 1 : Edit Accident Sequence Logic BETA. BETA, which may be used for further 2: Edit Base Case System Failure editing, displays or plots on HP laser or Epson Probabilities printer, the event tree specified by the Event 3: Edit System Identification Table logic and computes, displays and/or 4: Edit Problem Title prints the end or intermediate state probEdit Binary Conditionals 5: abilities according to damage criteria. It also 6: Display the Event Tree provides for changing nodal probabilities 7: Display Accident Sequence Probabilities within the event tree according to the Print Accident Sequence Probabilities 8: preceding sequences ("binary conditionals"). Save Data File 9: The size of event trees is essentially unlimited 10: Read in New Data File by its ability to branch and link with other 1 1 : Link this Event Tree to Secondary Tree(s) event trees. Work sessions may be saved to 12: Leave the Analysis Session floppy or hard disk for recall. Selections 1 to 5 allow data modifiSelect the Number Identifying Your Job cation and supplementation. Selection 6 displays the event tree. The tree will be Fig. 12.2-1 The Main Beta Menu

452

Appendix

correctly displayed, although it may be in parts depending upon how the events are input. Selection 7 displays the accident sequence probabilities; selection 8 prints them, and FTAPSUIT Select 1 selection 9 saves all of the information to a floppy or hard disk. Selection 10 reads in a new data file; .selection 11 links to a secondary tree and 12 exits the program..

_ FTAPLUS '; Select 1, 2, and 3

12.3 BNLDATA This folder contains three files: bnlgener.xls, bnlgener.wql, and referen.txt. The database, bnlgener is an eclectic collection of 1,311 failure rates from 31 references. The database is provided as a spread sheet in the Microsoft Excel 4 format (xls) and in Corel Quatro-Pro format (wql). This information is not provided in ASCII because of format scrambling and to use the search capabilities of either of the two spreadsheet programs. The references that are cited in the spreadsheet are provided in ASCII as file: referen.text.

12.4 FTAPSUIT

FN.II

Fault tree or equivalent analysis is key to PSA. Small logical structures may be evaluated by hand using the principles of Chapter 2 but at some point computer support is needed. Even for simple structures, uncertainty analysis by Monte Carlo methods requires a computer. However, most of the codes are proprietary or a fee is charged for their use. Fortunately a set of codes was made available3 for use on a personal computer. The suite consists of the following FORTRAN programs: 1,

2.

FTAPSUIT Selects

FTAPLUS Select 5 FNNJi

FTAPSUIT Select 7

IMPORT j->-FN.IO

/ FTAPSUIT Select 8

u, FN.MI MONTE

FTAP give it fault tree or equivalent input as linked Fig. 12.4-1 Procedure for Using Boolean equations, it will give the cutsets (Section FTAPSUIT 2.2), but does not numerically evaluate the probabilities. PREPROCESSOR modifies the FTAP punch file output for common cause and dependent analyses (conditional probabilities), remove complemented events, correct for mutually exclusive events. a

These codes were made available by Dr. Howard Lambert, FTA Associates, 3728 Brunei] Dr., Oakland, CA 94602, phone (510) 482-1492.

453

Appendix

3. 4. 5.

BUILD accepts a file from FTAP or PREPROCESSOR that specify events whose probabilities must be added for quantitative analysis. IMPORTANCE accepts the output from BUILD and calculates importance measures (Section 2.8) and provides input to the uncertainty analysis. MONTE performs a Monte Carlo analysis using uncertainties in the data to estimate uncertainties in the calculation of the system and subsystem failure probability.

The programs were written for a main frame computer using card input. To make the set of codes easier to use, I wrote auxiliary codes to organize the procedures and permit the user to provide input in comma-delimited format. This organizes the "deck" input and assures proper column placement of the data. Figure 12.4-1 shows the sequence of actions. Selections from FTAPSUIT are in the left column. The right column uses three selections from FTAPLUS and the rest are from the previous FORTRAN programs. Although the suite of programs can be run from the floppy disk, for reasons of speed and problem size, it is recommended to run from a hard disk. In DOS, type MD "directory name," enter, and cdV'directory name," enter. Type copy a:\*.* and the disk will be copied to that directory. Type FTAPSUIT and the screen shown in Figure 12.4-2 is presented. First, system information must be input. From FTAPSUIT, type 1 and enter. This starts FTAPLUS with its menu as shown in Figure 12.4-3. Select 1 and type a title for the problem; the default title is "Station Blackout from Loss of Offsite Power," unless you want to use this enter your title. Select 2 to enter a less than 7 character file name. This name is used throughout the suite with the extender being changed as shown in Figure 12.4-1. (In this figure F. stands for file name.) It is advisable to keep the name short because it is requested for the FORTRAN programs. The default designator is "DG" (diesel generator). Select 3 to input the linked logic sequences using a comma delimiter, no comma at the end, and enter to indicate the end of the line. Type # and hit enter to mark the end of input. For example, the test logic is: BLACKOUT,*,LOSP*NO-AC; NO-AC,*,A,B,C; A,+,DG-A,DG~A-M; B,+,DGB,DG-B-M; C,+,DG-C,DG-C-M;#; where the semicolon designates enter. Notice these equations are linked with BLACKOUT being the top event. This completes the preparation of FTAP input; selection 6 exits FTAPlus to return to the FTAPSUIT menu (Figure 12.4-2). Figure 12.4-1 shows tile FN.FI was created. This is an ASCII file which can be edited, if needed, with a text editor. The next step is to run FTAP by selection 2 from the FTAPSUIT menu shown in Figure 12.42. It asks you to enter the file name that was assigned in selection 2 from the FTAPlus menu. Do not give an extender. A "successful completion" sign indicates proper FTAP execution. At this point, the cutsets have been found and can be seen by reading file FN.FO with a text editor. While this qualitative analysis is useful, usually a quantitative analysis is needed. Figure A-1 shows that the qualitative analysis can be used as-constructed by going to BUILD via file FN.PCH or POSTPROCESS can be used to modify the operation and indicate conditional probabilities. The postprocessor reads the punch file from FTAP and generates an output file in a format which can be read by BUILD. It can execute commands not found in FTAP. Features of the postprocessor include: 454

Appendix.

Conducting common cause and dependent event analysis Dropping complemented events and performing the subsequent minimization Generating block files (i.e., a set of Boolean equations) for subsystems Eliminating mincutsets with mutually exclusive events Selection 3 from the FTAPSUIT menu (Figure 12.4-1) runs FTAPlus for preparing input for

FTA Associates FTAPlus Main Menu

Master Program for FTA Associates Codes 1. Prepare Input for FTAP 2. RunFTAP 3. Prepare Input for POSTPROCESSOR 4. Run POSTPROCESSOR 5. Run BUILD 6. Prepare Input for IMPORTANCE 7. Run IMPORTANCE 8. Run MONTE H. Help File

1: 2: 3: 4: 5: 6:

Provide Title for FTAP Provide File Name Input FTAP Tree Logic and Save Input Data for POSTPROCESSOR and Save Input FT Data for IMPORTANCE and Save Leave the Analysis Session Select the Number Identifying Your Job Fig. 12.4-3 FTAPlus Menu

Q- Quit Input designation of Task, Press ENTER

FTA Associates Postprocessor Input

Fig. 1'2.4-2 Menu for FTAPSUIT

1: Eliminate Complemented Events the postprocessor (Figure 12.4-4). To print (NOCMPL) the contents of the blockfile, the postprocessor 2: Print Mincuts in FTAP Format (PRTDNF) input must contain either the command 3: Same as 2 and Boole Equa. for Top Event PRTDNF or FRMBLK (selections 2 and 3 (FRMBLK) respectively). The command PRTDNF (print 4: SORT equation in disjunctive normal form) allows 5: Mutually Exclusive Input (MEX) you display the contents of a punch file in 6: Substitute Cutsets for Dependencies (SUB) readable form. FRMBLK (form block) is 7: Exit Menu required to generate an FTAP input file. The command NOCMPL drops complemented Select the Number Identifying Your Job events (i.e., assumes that they are true) and performs the subsequent minimization. The Fig. 12.4-4 Postprocessor Menu command SORT sorts cutsets according to order. It is necessary to sort the punch file to run IMPORTANCE if cutsets are not listed according to order in the punch file (which occurs when probabilistically culling in FTAP using the IMPORT instruction).

455

MEX and SUB are optional commands. MEX command must precede the SUB command. The MEX command sets to false, basic events that are pairwise mutually exclusive. For the SUB command, the user identifies sets of basic events within cutsets (original sets) that are to be replaced by another set of basic events (substituted sets). The SUB command accounts for basic events within cutsets that have either a common cause or statistical dependency. After selecting the MEX command (selection 5) the comma delimited input consists of groups of basic events that are pairwise mutually exclusive. To extend the group to the next and subsequent lines, the first field must be blank. Up to 100 names per group are allowed with a new group starting when a non-blank character is encountered in the first field. The number of pairs that are mutually exclusive is: n!/[(n-2)! *2!], where n is the number of basic events in the group. An example for the plant blackout fault tree is: DG-A-M,DG-B~M,DG-C-M; (where ";" means enter). Selection 6 (Figure A-4) executes the SUB command. The comma-delimited input alternates between the cutset to be replaced and the cutset replacing it. For example for the plant blackout problem, the input is: DG-A,DG-B,DG-C;DG-A,DG~B/A,DG-C/A&B;DG~A,DG~B;DG-A,DGB/A;DG-A,DG-C;DG-A,DG-C/A;DG-B,DG~C;DG-B,DG-C/B. The actual input to BUILD alternates lines with * and ** to identify lines to be replaced with replacing lines, but this bookkeeping is done automatically by FTAPlus. The original set of basic events and the substituted set cannot exceed 99 basic events. The SUB command completes the postprocessor input. Select 7 to exit the postprocessor menu and 6 to exit FTAPlus for the FTAPSUIT menu. Select 4 from this menu and POST (postprocessor) begins by requesting the data input file name (e.g., dg.pi - prepared by FTAPlus), the punch file name (e.g., dg.pch), the block file name (e.g., dg.blk) and the name to be assigned to the new punch file (e.g., dgn.pch). Two outputs are produced: FN.BLK and FNN.PCH. Select 5 from the FTAPSUIT menu and BUILD starts by requesting the puncbiile name (e.g., dgnpch or dgpch depending on whether you want to run the original fault tree the postprocessed fault tree. It requests the name to be given the importance input file (e.g., dg.ii). The last request regards the type of input. Option 5 is pure probability, option 1 is failure rate. BUILD generates file FN.II for editing. Selection 6 goes to FTAPlus, from which menu 5 is selected, to provide the information needed for IMPORT. This program presents event names as given in FTAP and POST and requests failure rates or probabilities (e-format), uncertainty (f-format), and an event description. Each time this set is given, it presents the next event name until all events are specified. Then it returns to the main FTAPlus menu to be exited by selecting 6 to go to the FTAPSUIT menu. Selection 7 causes IMPORT (importance) to start by requesting the name of the input file FN.II (e.g., dgn.ii). The importance output is contained in the FN.IO file. The output needed by MONTE is FN.MI. Selection 8 from the FTAPSUIT menu runs MONTE (Monte Carlo). It requests the name of the input file, FN.MI (e.g., dgn.mi). The Monte Carlo analysis is contained in file FN.MO.

456

Appendix

12.5 Lambda

Lambda - Statistical Functions

To run Lambda go to the directory 1) Upper Bound Failure Rate (Inverse Chi2) containing the distribution files and type 2) Upper Bound Probability (Inverse "Lambda." A banner announces the program. Binomial) The next screen explains the program that does 3) Cumulative Chi-Squared several calculations (Figure 12.5-1). 4) Inverse Cumulative Chi-Squared Selection 1 performs a one-sided, 5) Inverse Cumulative F-number fractional confidence bound of the failure rate 6) Cumulative Gaussian (normal) based on Chi-Squared estimation (Section 7) Inverse Cumulative Gaussian (normal) 2.5.3.1). When this selection is made, it asks 8) Gamma and Factorial Integer and Half you to specify your confidence bound, the Integer Functions number of component years of experience, and 9) Exit the number of failures. For example, to Select your job number estimate the failure rate for a component that Fig. 12.5-1 Menu for Lambda has had no failures in 7,015 component-years of experience with 50% confidence: input "1" (for chi-squared), input 0.5 (50% confidence), input 7015 (component years of experience), and input "0" (number of failures). The program answers: A(50%) = 9.883E-5/years. Rerun the program for 90% confidence and get: A(90%) = 3.282E-4/years. Selection 2 is a similar calculation using the F-Number method (Section 2.5.3.2). Selection 3 calculates the integral over the Chi-Squared distribution. When selected, you are requested to input the upper limit of integration and the number of degrees of Brookhaven National Laboratory Microcomputer Club freedom. Selection 4 is the inverse calculation and is part of 1 Length 13 Electrical Charge the Selection 1 calculation. You 14 Magnetic Field Int. 2 Area are requested to input the 3 Volume 15 Magnetic Field Density confidence, and the degrees of 4 Mass 16 Radioactivity freedom. The answer is the 5 Force 37 Dose inverse cumulative Chi-Squared. 6 Time 18 10's Power Prefixes Selection 5 is part of the Selection 7 Power 19 Temperature 2 calculation. You input the 20 Constants 8 Energy confidence limit (equation 2.5-34) 21 Relativity 9 Pressure and the nu values to get the F22 10 Viscosity Quit Number. Selection 6 gives the 11 Velocity integral over the normal 12 Acceleration distribution from -4 is 2.4E-4, >10 is, >40 is 5.9E-6, >100 is 6.0E7. Hence the probability of 3 is 2.4E-4, 6 is 8.2E-5, 30 is 5.9E-6,60 IE-O ,is 6.0E-7. The mean is 1.4E-5/(year-plant). 3a. Devise an alternative to logarithmic plotting that is more familiar that compresses the range of data. Answer: Figure 1.4.3-5 shows volume scaling. Another Fig. 15,1.2-1 Redraw of alternative is area scaling. Figure I 4.3-1 3b. Apply your method to Zion in Figure 1.4.3-6. Answer: The results are shown in Figure 15.1.3-1. 4a. 10CFR50 Appendix I gives the value of a person-rem as $ 1,000, The report, Biological Effects of Ionizing Radiation (BEIR, 1972) assesses about LOCA with failure!; 10,000 person-rem per death (statistically-not exposed of safety injection 3% to an individual). Given this inforsite power ,.

,

, .

„

.

. Transients

mation, what is Althe cost of a death with failure r

j-

•

r,

ofLTDHR ATWS1S%

from radiation? 4% Answer: Given $l,000/rem and 10,000 rem/death, the cost of a human death from radiation is: $10 M,

transients 18% X

All

others

LOCAs with failure of long term decay heat removal (tTDHR) inducting event V 59%

Fig.

493

J5.1.3-1 Comparing by Area

Answers to Problems

4b. At Pickett's charge at Gettysburg, approximately 30,000 soldiers died in 30 minutes. What is the expenditure rate per minute if the same life equivalence were used? Answer: Using the cost of a life for radiation, the cost was $ 3E11. The expenditure rate was $ lElO/minute or 10 billion dollars/minute. Clearly if soldier lives were valued the same as radiation death, no government could afford to go to war. 5a. Discuss worker vs public risk. Answer: Humans accept a greater voluntary risk than involuntary risk. Part of this argument is that one should be free to commit suicide whether with a gun or in "sports." A counter argument is that if the suicide is not successful, the cost of health care may fall on society. The same is true of smoking or drinking alcohol, although in the case of cigarette smoking, the manufacturers may have to pay the health costs. It seems that there is a tendency to take risk but not want to pay the cost of the risk taking. Figure 1.4.4-1 shows that the ratio of voluntary to involuntary risk is 1,000 to 1, The reason why worker risks are higher than involuntary risks is that worker risks are presumed to be voluntary. It is true that a worker understands that there are risks associated with the job, but the worker has aptitude and training that presumably makes the job higher paying and perhaps more gratifying than other alternatives. 5b. Should non-repository workers be treated as public or workers from a risk standpoint? Answer: The repository workers accept certain risks (primarily that of a miner) as a condition of employment and the other workers accept other risks as a condition of employment. It seems reasonable that the non-repository workers should be treated as public for all risks that are not part of their conditions of employment. Similarly, repository workers should be treated as public for all risks that are not a condition of their employment. 6. Discuss why the EPZ should be independent of plant size, safety features, demography and meteorology. Answer: The only reason I can think of for making the EPZ independent of plant size, safety features, demography and meteorology is the convenience of emergency planners. Such would take no consideration for the hazard a plant poses; it would favor hazardous activity and penalize safe activity. 7. Compare the risk of evacuation with that of radiation exposure at TMI-2. Answer: The automobile death rate is about lE-7/passenger mile. If 25,000 people evacuate 20 miles, this is 5E5 passenger miles, hence, the risk is 5E5*lE-7 = 0.05 deaths. The radiation exposure is 2.5E4*5E-4*48 = 600 person-rem. Using information from problem 4, the estimated deaths from radiation is 600* 1E-4 = 0.06. About the same. The risk from radiation may be over estimated because the radiation level was measured close to the plant; on the other hand, the traffic fatality estimate may be high because of police presence and slow driving. 8a. The government is charged by the Constitution with a responsibility for the public welfare, Discuss the government's responsibility in controlling the risks in society. Answer: The ambiguity comes in the meaning of public welfare. It may mean improving economic and environmental conditions of the public; it may mean protecting the public from their own folly generally by prohibiting certain actions and activities. Some people wish to engage in hazardous activities without accepting the responsibility for their actions. The current tendency in the courts is to absolve them of this responsibility and place the burden on anything with "deep 494

Answers to Problems

pockets" however nebulously connected with the hazard. Primarily this denies that the risk taker understood the risk. 8b. Tobacco is not subject to the Delaney Amendment that bans material that can be demonstrated to cause cancer in animals regardless of the quantity of material used in the tests. Why aren't all materials subject to the same rules? Answer: Tobacco is an example (this problem was written 10 years ago before the recent court decisions). In the '1930s, it was generally acknowledged that tobacco was unhealthful. Cigarettes were called "coffin nails." There was a popular song about driving nails in you coffin. Nevertheless courts have taken the attitude that the risk was not understood, and that the tobacco companies acted to gain addicts especially among the youth. Tobacco is not subject to the Delaney Amendment because Congress chose to protect the tobacco growers. In a more ideal world, laws should apply equally to all substances regardless of economic interests. Moreover, laws should have a scientific basis in reality.

15.2 Chapter 2 1. The control rods in a hypothetical reactor have the pattern shown , 2 j in Figure 15.2.1-1. Based on plant experience, it is determined that the 4 5 6 ? g probability of a rod failing to insert is 0.0I/plant-year. Assuming that if 3 9 ' J o ' H " * j nearest-neighbor rods fail to insert, core damage will result. What is the ; ~ ; ' probability of core damage from failure to scram from control rod sticking? 23 24 25 26 27 Answer The counting technique uses pivot points. The 3 NN unique 28 29 30 combinations for 1 are: 1,4,5; 1,5,6; 1,2,6. 2 has 6 combinations, 3 has 3. 4, 5, 6, 7 and 8 have 4. 9, 10,11, 12, 13, 14, 17, 18, 19, 20, 24 and 25 have ^ ^Pattern 2. 15, 16, 21, 23, and 26 have 1. The total number of unique 3 NN combinations is 61; the probability of 3 rods failing is 1E-6, hence the probability of 3 NN failing on a scram request is 6,1E-5. 2. The Boolean equation for the probability of a chemical process system failure is: R = A*(B4C*(D+E*(B+F*G+C). Using Table 2.2-1, factor the equation into a sum of products to get the mincut representation with each of the products representing an accident sequence. Answer: The cutsets are: A*B + A*C*D + A*C*E. The terms A*C*E*B and A*C*E*F*G are contained by the A*C*E term. 3. The probability that a system will fail is the sum of the following probabilities: 0.1, 0.2, 0.3, 0.4, and 0.5. What is the probability of failure? Answer: The easiest way is to calculate the probability of not failing and subtract it from 1. P = i-(.9*.8*.7*.6*.5) = 0.8488. 4. The probabilities for the equation in Problem 2 are: A = lE-3/y, B = 4E-3, C = 7E-4, D = 0.1, E = 0.5, F = 0.25 and G = 0.034. What is the value of R? What is the probability of each of the sequences? Answer: The probabilities of the sequences are A*B = JE-3/y* 4E-3 = 4E-6/y; A*C*D = IE-3/y*7E-4*0.1/y = 7E-8/y; A*C*E = lE-3/y*7E-4*0.5 = 3.5E-7/y. R = 4.42E-6/y. 5. Using the information and result of Problem 4, calculate the Birnbaum, Inspection, 495

Answers to Problems

Fussell-Vesely, Risk Reduction Worth Ratio, Risk Reduction Worth Increment, Risk Achievement Worth Ratio and Risk Achievement Worth Increment for each of the components A through G. Do your results agree with the equivalences in Table 2.8-1? Answer: R = A*B + A*C*D + A*C*E. The Birnbaum importance of A = 4E-3 + 7E-4*0.1+7E-4*0.5 = 4.42E-3. Similarly the other Birnbaum importances are: B = 1E-3, C = 6E-4, D = 7E-7, E = 7E-7, F = 0, G = 0. Inspection importance is: A = 4.42E-6, B = 4E-6, C = 4.2E-7, D - 7E-8, E = 3.5E-7, F = 0, G = 0. Fussel-Vesely is Inspection Importance divided by risk, hence: A = 1, B = 0.9, C = 9.5E-2, D = 1.6E-3, E = 0.7.9E-3, F = 0, G = 0. The Risk Reduction Worth Ratio is the ratio of risk with the component failed (set to 1) to the risk unfailed: A = 1000, B = 226, C = 136, D = 1. 14, E = 1.08, F = 0, G = 0. The Risk Reduction Worth Increment is the risk with the component failed minus the risk. A = 4.4E-3, B = 1E-3, C = 6E-4, D = 6.3E-7, E = 3.5E-7, F = 0, G - 0. The Risk Achievement Worth Ratio is the ratio of the risk with the component unfailed (set to 0) to the risk A = 0, B = 0.095, C = 0.9, D = 0.98, E = 0.92, F = 1 , G = 1. The Risk Achievement Worth Increment is the risk minus the failed component: A = 4.4E-6, B = 4E-6, C = 4.2E-7, D = 7E8, E = 3.5E-7, F = 0, G = 0. Yes the results agree with the table. Spot checking: RRWI{C) = Birnbaum(C) - Inspection(C) = 6E-4. 6. In Section 2.5.4, we found the availability of a repairable emergency generator (EG) by Markov methods. If a plant requires that two identical, independent EGs must both work for time T for success. What is the probability of this? Assume the failure rates are A L A,2, and the repair rates are u, ji2. Answer: Equation 2.5-42 gives the probability of an EG operating: Pj = (u,+ X,*exp[(It+Uj)*T] } /(Aj+jUj). The independent probability of the other working in the same time period is PI = 1 u,-f~ X2*exp[-(A.2+fj2)*T] } /(A2+fj;2). The probability of both working at the same time is PcomWnWI

15.3 Chapter 3 Reactor

Containment

Cora

Containment

Core

Break Sub critical over-pressure coo/ing over-pressure coaling la. Transform the event tree Pipe {*) (OS) (ECt) (C02) (C01) fBcnf of Figure 3.4.5-2 into several fault i J, core cooled trees for each plant damage state '•" ' ——2. slow malt nanodt 3 = not applicable noting that end points 1, 3 and 6; 2,4 [-———— 3, core cooled and 7; 5, 8,9, and 10 lead to the same ' '— 4. slow melt damage state. : Answer: End points 1, 3, and | 6, core cooled Start '•"• • -—-..— 7. stow melt 6 are success paths which are not modeled by a fault tree. The fault Fail I tree for slow melt is Figure 15.3.1-1. — i i — in Unit Ib. Find the cutsets of each fault tree. Answer: The equations Fig. 3.4.5-2 Large LOCA as a Function Event Tree (adapted from NUREG/CR-2300) are: Slow Melt = PB*ECR, and Melt = PB*ECl-fPB*RS. Ic. Assuming the following failure rates: PB = 3.1E-2, RS = l.OE-5, CO1 = 2.3E-2, ECI

496

Answers to Problems

= 3.2E-3, CO2 = 0.1, ECR = 2.5E-2, calculate the Birnbaum, Inspection and . Slow Melt Risk Achievement Worth Ratio for each system including the initiator. Answer: Slow Melt = 3.1E-2*2.5E-2 = 7.75E-4/y. Melt = 3.1E2*(3.2E-3+lE-5) = lE-4/y. Let Slow Melt Birnbaum of PB be represented PB by B(SM, PB) = 2.5E-2, B(SM, ECR) = 3.1E-2. Similarly for Melt, B(M, PB) = 3.2E-3, B(M, ECI) = 3.1E-2, B(M, RS) = 3.1E-2. For Inspection ECR CO1 Importance: I(SM, PB) = 7.75E-4,1(SM, ECR) = 7.75E-4,1(M, PB) = 9.9E5,1(M, ECI) = 99E-5,1(M, RS) = 3.1E-7. For Risk Achievement Worth CO2 ECR Ratio: RAWR(SM, PB) = 32, RAWR(SM, ECR) = 40, RAWR(M, PB) = Fig. 15.3.1-I Slow 32, RAWR(S, ECI) = 320, and RAWR(S, RS) = 320 Melt Fault Tree 2a. Construct a Reliability Block Diagram (RBD) of the simple injection system shown in Figure 3.4.4-6. Answer: The RBD is Melt shown in Figure 15.3.2-1. 2b. Discuss the relative merits of these models and the fault tree model of the same system. PB Answer: The RBD is a clear logical figure in which water flows from left to right. Redundancies such as Valves B and C ECI RS are shown as parallel paths. The RBD uses positive, i.e., success logic. It is anachronistic to introduce negative logic into an RBD CO1 : ECI RS CO1 such a Valve Closes. A fault tree looks nothing like the flow Fig. 15.3.1-2 Melt Fault Tree diagram. The logic is reversed to look for failure. There is no success path. Its large set of symbols Valve B[ allows easy expression of the most Opens | Water > SIS Pump J Valve £ I Valve A complex systems. Supply Actuates I Runs • Closes Opens Valve c] Opens ; 2c. Assuming the following Fig. 15.3.2-1 RBD of a Simple Injection System failure probabilities: pump = 0.01, SIS = 1.5E-3, valves A through E = 4.3E-3, evaluate each of your models to determine the probability of this system functioning on demand. Calculate the Birnbaum, Inspection and Risk Achievement Worth Ratio for each of the components using which ever model you prefer. (Once you get the cutsets, it does not matter which model was used as long as it is a correct system model.) Answer: The success probability of the RBD is: 9.985E-1* 9.9E-1 *9.957E-1 *9.957E-1 *9,999815E-1 *9.957E-1 = 0.9758. The importance measures are for negative logic. The success of the train is SI = SIS + P + VE + VA + (VB*VC) + VD. Insert numbers and test and get 2.42E-2 which is the same answer as by success logic. Birnbaum importance is B(SIS) = 1, B(P) =1, B(VE) =1, B(VA) =1, B(VB) = 4.3E-3, B(P) = 4.3E-3, B(VD) =1. Inspection Importance is: I(SIS) = 1.5E3,1(P) = .01,1(VA) = 4.3E-3,1(VB) = 1.8E-5,1(VC) = 1.8E-5,1(VD) = 4.3E-3. RAWR(SIS) = 41, RAWR(P) = 41, RAWR(VE) = 41, RAWR(VA) = 41, RAWR(VB) = 1.177, RAWR(VC) = 1.177, andRAWR(VD) = 41. 2d. Rark order the systems for-each importance measure. Answer: the Birnbaum rank order where [ ] encloses items of the same rank is: [SIS, P, VE, VA, VD], [VB, VC]; Inspection is: P, [VA, VD], SIS, [VB, VC]; RAWR is: [SIS, P, VE, VA, VD],[VB, VC].

Q

0 Q

497

Answers to Problems

2e, Why doesn't each measure result in the same ordering? Discuss which is the "best measure. Answer: They don't give the same result because they are not measuring the same thing. Bimbaum and RAWR are similar because the both show what happens when a component's failure rate is set to 1. This statement is only approximately true for more complex systems than the simple RBD. A basic difference is RAWR is divided by the risk but this just shifts the scale. In this case Inspection seems superior because it distinguishes between more of the components except for those that are identical with identical roles. It introduces a weighting by the failure rate of the component which gives higher priority to those with a high failure rate. 3a. In the ZIP, members of a redundant train are treated as identical and for this reason correlated. In such case, the means and variances do not propagate as independent distributions and recourse is made to Equations 2.7-24 and 2.7-26. For the "V" sequence (release bypassing containment), the mean failure rate of an MOV if 1.4E-8/hr with a variance of 5,3E-15/hr*hr. For two doubly redundant valves, what is the mean failure rate and variance? Answer: The mean of the combination is = 2. The variance of the combination u(Q) = 2 +u(q). Hence = 2E-16/hr2. u(Q) = 2E-16/hr2 + 5.3E-l5/hr2 = S.SE-lS/hr2. 3b. What is the beta factor under this assumption of the valves being identical? Answer: It is p = A/lc. But if the common-cause failure rate is the same as the component failure rate, A = 1 and A,c = °° = A,. This is impossible. 3c, Discuss your opinion of the validity of the identical assumption and suggest experimental tests of the validity of such strong coupling. Answer: It is unrealistic. No components are identical, but even if they were the causes of random failure in component are not correlated to the other component because they are defined to be random. However, components can fail at the same time from deterministic coupling such as fire, missile, common utilities etc. 4a. Prepare a FMECA for Valve A (a motor-operated valve - MOV) in Figure 3.4,4-6. Answer: The FMEA is presented in Table 15.3.4-1. 4b. How do you handle the redundancy between Valve B and Valve C in a FMECA? Note Failure of redundant diesel emergency this problem requires some understanding of MOVs i power system and how they can fail. ( j Answer: You can treat them as one Bothd s work staA>r component in the component column and prepare the '^ FMECA for ways they can fail together. For random | 1 failure of both valves in a mission time,' estimate the ~ 1 OGjA ; 06 DQ B ' Accumulator, \ Pipe failure probability as one-half the failure rate of one /*N times the probability of ailing in the mission time of ,

,

.

tne Otner.

.Engine

--

_

1

,

Starting i i Contml

5a. Prepare a fault tree of a dual emergency "**" power system, considering that the compressed air !""!._ J Generator used for starting the diesels is a separate system F/g. is.3.5-1 Fault Tree of Emergency which may be a common-cause failure to start the Electric Power 498

Valves

Answers to Problems

diesels. Answer: Figure 15.3.5-1. 5b. Using A, and A2 f°r tne failure rates and u, and u 2 f°r tne repair rates, what is the frequency of both systems working? One or the other? None? Table 15.3.4-1 Failure Modes Effects Analysis for Valve A in Figure 3.4.4-6 Effect Mitigation Failure mode Component Divert fluid from Valve body crack Valve Failure Periodic test and injection inspection Valve flapper Disconnect from Test or inspect by disassembly. shaft, situation ambiguous Foreign material Strainer upstream, test and blocking the ability inspection to open Fails to block flow Valve seat Need leakage taps on when closed. system to determine if Possible leakage of there is leakage between SIS fluid into system series valves. Sense and reduced temperature of pipe. operability. Inspection. Bearing Motor cannot open Shorts can be sensed by Motor Failure valve ground leakage. Shorted winding Bearing failure can be detected by test Open winding Open winding can be sensed by winding resistance. Coupling slipping, Cannot open valve Motor current when in Shaft coupling sheared pin or key operation, inspection Control switches Valve binding, in Limit switch failure Test and inspection ability to move valve Improper limit switch In ability to move Test and inspection valve setting .„„ , .„ ., _ . , j

Answer: Ignore the Starting air system. The fault tree does not model repair. The frequency of both systems failing is: 1/2*A1*A2 *t, where t is the mission time, hence, the frequency of both systems working is l-A,*^ *t. The frequency of one or the other (not both) working is 1- A,+12 + 1 /2*A,*A,2*t. (Assuming that A,, A 2 «l.) 5c. Compare these results with the Markov model prepared in Section 2.5.4. Under what conditions do the two methods agree? Answer: The Markov model was prepared for one diesel having two states: working and failed. For two diesels, the probability of both failing at the same time is A = 1/2*A.1*X2*t, where t is 499

Answers to Problems

the mission time. If the repair rate is short ji«A, the failure probability (Equation 2,5-42) is: Q = exp(-A*t). When expanded it is Q = A,*t. The failure frequency is A, = l/2*A|*l2*t 6. The "gedanken" experiment in Section 3,4.4.2 results in equation 3.4.4-2 suggesting the operations of summation and multiplication in the algebraic sense - not as probabilities. Since this is a simulation why are not the results correct until given the probability interpretation? Hint: Refer to the Venn Diagram discussion (Section 2.2). Answer: It is necessary in taking the summation that overlapping areas be removed to get the probability interpretation. 7a. Refer to the discussion of Problem 7 at the end of Chapter 3. Develop a relationship that shows the improvement that may be achieved by staggered testing. Answer: Referring to Figure 3.7-2, we assume the failure probability increases linearly from 0 to some amount with a slope a. Pa = a*t and Pb = a*(T-ti+t) for the time interval 0 S

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Fig. 15,5.2-1 The Percolator Scheme

diagram that includes set A and not set A. Therefore it is all inclusive. I have tried to use this for completeness but the problem is that it is no help in specifying systems and causes of failure. 4. In the WASH-1400 analyses of nuclear power accidents, it was calculated that it is possible to overpressure and rupture the containment. Discuss whether this is better or worse than a pressure

503

Answers to Problems

relief that releases radioactivity but prevents the pressure from exceeding the rupture point. Spent fuel reprocessing plants are designed to release filtered and processed gases. Typically the final filters are large containers of sand or HEPA (high efficiency particulate air) filters. Discuss filtered containment with consideration for possible failure modes of the filter. Answer: It seems to me the Water Refriger P. relief Scrub- Flare & valve- ber enters ation stack argument is whether or not to design for failure of the MIC blowout containment. It is reasonable to design the containment with a blowout panel to blowout before the containment fails and to discharge the gases through scrubbers and HEPA filters before exhausting the stack. This is essentially the practice of chemical processing in which the effluent is hazardous and cannot be contained, therefore, it is processed to make it benign. 5. Early BWRs used an isolation condenser, although such is not specific to the direct cycle. This Fig. 15,6.1-1 Bhopal Accident Event Tree device removes decay heat by steam flow through a heat exchanger the other side of which is water vented to the atmosphere. Discuss the relative merits of such a boiler. Answer: There are obvious merits in using an isolation condenser because it is being included in some of the advanced reactor designs. ** FTAP INPUT ** Failure to Inject Fault tree Al + A B Bl 15.6 Chapter 7 1. Prepare an event tree diagram of the Bhopal accident. Answer: See Figure 15.6.1-1. 2. Use FTAPSUIT to calculate the fault tree shown in Figure 3.4.4-7. For data useA = C = D = E = H= l.OE-2/d for valve failure to open; for failure of the SIS signal: B = 1 .OE-4/d, for a pump failing to start: F = 2.0E-2/d, and for a pump failing to run after it starts: G = 5E-3/d. Answer: The input for the fault tree is shown in Figure 15.6.2-1. Running IMPORTANCE gave 4.93E-2. The AND gate would require a mission time if these were failure rates but since they are failure per demand, the units are correct.

15.7 Chapter 8 1. Suppose an interstate highway passes 1 km perpen-

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Fig. 15.6.2-1 Failure to Inject Fault Tree Input

Answers to Problems

dicular distance from a nuclear power plant control room air intake on which 10 trucks/day pass carrying 10 tons of chlorine each. Assume the probability of truck accident is constant at l.OE-8/mi, but if an accident occurs, the full cargo is released and the chlorine flashes to a gas. Assume that the winds are isotropically distributed with mean values of 5 mph and Pasquill "F" stability class. What is the probability of exceeding Regulatory Guide 1.78 criteria for chlorine of 45 mg/m3 (15 ppm), Answer: The geometry is a line passing to within a kilometer of the plant. The probability of a release in any mile is l.OE-8. For a plane geometry the probability that the wind is blowing toward a 0,1 km wide plant is 0.1/(2*7i:*r), where r = V"(x2+d2). Equation 8.3-1 shows an exponential dependence on r, and oh. I fit the equation oh = 37*ra877. For the denominator, I fit o y = 140*ra5. These arc assembled into the BASIC code CHLOR to calculate the probability weighted average %/Q. The answer from running the program is <x>/Q = 1.25E-16. However 100 tons per day are transported past the plant to give a probability of 4. 15E-6 gm/y reaching the plant. The NRC criterion is 0.045 gm so the probability of 9.2E-5/y of exceeding the criterion. The computer program is included on the disk, 2a. How long can you remain in a very large flat field that is contaminated with radioactivity at a density of 1 curie/rn2 emitting gamma rays of 0.6 MeV mean energy before you exceed 10CFR 100 limits for whole body? Answer: Assume the receptor is at 1 m, : "eceP*or Etherington, 1958 gives the total attenuation : - -• coefficient in air: u., = 0.0804 cnrVgm, and the energy \z 2 absorption coefficient fie = 0.03 11 cm /gm for tissue. ( ~ :&& . f These coefficients must be multiplied by the density -- _ Fallout field of air and tissue, respectively. Figure 15.7.2-1 depicts Fig j 5j^-l A Radiation Fallout Field a radiation fallout field. Let C be the curie activity/m2. The radiation into a unit area Q = c/2 * Jexp( -u, */?) *dR/R (1572-!) receptor at z = 1 m above the ground. The area is emitting C*r*dr*d0 gammas/s. These are z attenuated in the air as exp(-u*R) and ~n °°r , JN , , . , _ _ - ON . „ , „ _ a,,. i:* ' . =C/2* 15.7.2-2) r JJ exp(-f)*

Probabilistic Safety Assessment in the Chemical and Nuclear Industries

Probabilistic safety assessment in the chemical and nuclear industries

Probabilistic Safety Assessment in the Chemical and Nuclear Industries, First Edition